WO2022259774A1 - 水性塗料組成物、塗膜及び塗膜の製造方法 - Google Patents
水性塗料組成物、塗膜及び塗膜の製造方法 Download PDFInfo
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- WO2022259774A1 WO2022259774A1 PCT/JP2022/018535 JP2022018535W WO2022259774A1 WO 2022259774 A1 WO2022259774 A1 WO 2022259774A1 JP 2022018535 W JP2022018535 W JP 2022018535W WO 2022259774 A1 WO2022259774 A1 WO 2022259774A1
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- OWLILVLEVSCTFV-UHFFFAOYSA-N magnesium oxocopper oxygen(2-) Chemical compound [Cu]=O.[O-2].[Mg+2] OWLILVLEVSCTFV-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- NJJQMCFHENWAGE-UHFFFAOYSA-N manganese yttrium Chemical compound [Mn].[Y] NJJQMCFHENWAGE-UHFFFAOYSA-N 0.000 description 1
- LDKODPFTYRRMSG-UHFFFAOYSA-N manganese(2+) oxobismuthanylium oxygen(2-) Chemical compound [O-2].[Mn+2].[Bi+]=O LDKODPFTYRRMSG-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 1
- XJINZNWPEQMMBV-UHFFFAOYSA-N n-methylhexan-1-amine Chemical compound CCCCCCNC XJINZNWPEQMMBV-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- ZZSIDSMUTXFKNS-UHFFFAOYSA-N perylene red Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=C(OC=5C=CC=CC=5)C=1)C(=O)C2=CC(OC=1C=CC=CC=1)=C3C(C(OC=1C=CC=CC=1)=CC1=C2C(C(N(C=3C(=CC=CC=3C(C)C)C(C)C)C1=O)=O)=C1)=C2C4=C1OC1=CC=CC=C1 ZZSIDSMUTXFKNS-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- VUNPWIPIOOMCPT-UHFFFAOYSA-N piperidin-3-ylmethanol Chemical compound OCC1CCCNC1 VUNPWIPIOOMCPT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- MRXVCTWDXRBVLW-UHFFFAOYSA-N prop-2-enoylsulfamic acid Chemical compound OS(=O)(=O)NC(=O)C=C MRXVCTWDXRBVLW-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- OJTDGPLHRSZIAV-UHFFFAOYSA-N propane-1,2-diol Chemical compound CC(O)CO.CC(O)CO OJTDGPLHRSZIAV-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- 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
-
- 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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D5/02—Emulsion paints including aerosols
-
- 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
Definitions
- the present disclosure relates to a water-based paint composition, a coating film, and a method for producing a coating film.
- Coated steel sheets that are coated on metal substrates such as cold-rolled steel sheets and plated steel sheets and then subjected to molding are also called pre-coated steel sheets (hereinafter also referred to as "PCM"), and are used in shutters, roofs, doors, and so on. Building materials such as roofs and sidings; exterior materials for electrical equipment such as cooler outdoor units; and interior materials.
- the precoated steel sheet is usually produced by applying a coating composition to the surface of the metal substrate and heating (baking) it at 200 to 270° C. for 30 to 60 seconds to form a coating film. , and then subjected to molding. Therefore, the coating film of the precoated steel sheet is required to have workability to the extent that cracks and peeling do not occur during processing, and hardness to the extent that scratches and dents do not occur.
- the coating composition is a one-component coating composition in which a main agent containing a film-forming resin and a curing agent containing a cross-linking agent coexist in the same system, and the main agent and the curing agent are stored separately,
- a two-component paint composition that is used by mixing at the time of use.
- the two-component coating composition does not mix the main agent and the curing agent until just before use, and is superior in storage stability to the one-component coating composition.
- Patent Document 1 Various proposals have been made for such a one-component water-based coating composition. It has been proposed to neutralize carboxyl groups contained in a hydroxyl group- and carboxyl group-containing acrylic copolymer with an amine compound (Patent Document 1). It also contains hydroxyl group-containing (meth)acrylic acid esters, carboxyl group-containing vinyl monomers, long-chain alkyl group-containing (meth)acrylic acid esters, copolymers of vinyl monomers, water-soluble amino resins, and aqueous media. In a water-soluble acrylic paint composition, it has been proposed to neutralize the carboxyl groups of a hydroxyl group- and carboxyl group-containing acrylic copolymer using an amine compound (Patent Document 2).
- a hydroxyl group- and carboxyl group-containing acrylic resin having a glass transition point in the range of -10°C to 80°C a hydroxyl group- and carboxyl group-containing acrylic resin having a glass transition point in the range of -50°C to 20°C, an aqueous amino resin, a base
- a hydroxyl group- and carboxyl group-containing acrylic resin having a glass transition point in the range of -50°C to 20°C an aqueous amino resin
- Patent Document 3 It has been proposed to neutralize the carboxyl groups of a hydroxyl group- and carboxyl group-containing acrylic resin with a basic compound in an aqueous coating composition for metal coating containing a polar compound and an aqueous medium.
- Patent Document 4 proposes a water-based paint composition containing a water-based resin, a melamine resin, and a phosphoric acid ester catalyst as a weak acid catalyst, and proposes neutralizing the water-based resin using a basic compound (Patent Document 4). Reference 4).
- the main agent and the curing agent coexist in the same system.
- the reactivity is lowered for the purpose of improving the storage stability of the coating composition, the physical properties of the coating film are lowered. Therefore, it has been very difficult to achieve both storage stability and coating film properties in a one-component coating composition.
- the present inventors have made extensive studies to solve these problems, and have found that a full alkyl melamine resin is used as a cross-linking agent, and a sulfonic acid compound and an amine compound are mixed so as to achieve a specific neutralization rate.
- a full alkyl melamine resin is used as a cross-linking agent, and a sulfonic acid compound and an amine compound are mixed so as to achieve a specific neutralization rate.
- high storage stability can be achieved, and even when painting is performed under the high temperature and short time conditions peculiar to precoated steel sheets, good physical properties of the coating film ( In particular, it was found that workability (adhesion, crack resistance), scratch resistance) can be exhibited, and a water-based coating composition and a method for producing a coating film according to the present disclosure were completed.
- the present disclosure provides a water-based coating composition that is excellent in storage stability even if it is a one-pack type, and that can form a coating film with good workability such as bending and crack resistance and scratch resistance during processing. Make it an issue.
- An aqueous coating composition comprising a coating film-forming resin (A), a cross-linking agent (B), a sulfonic acid compound (C) and an amine compound (D),
- the coating film-forming resin (A) contains an acrylic resin (A1), the coating film-forming resin (A) has a hydroxyl value of 5 mgKOH/g or more and 35 mgKOH/g or less;
- the cross-linking agent (B) contains a full alkyl melamine resin (B1), A water-based coating composition, wherein the amine compound (D) has a neutralization rate of 100% or more and 1,300% or less of the acid groups of the sulfonic acid compound (C) in terms of moles.
- the shear viscosity measured at a shear rate of 0.01 s ⁇ 1 is 30,000 mPa s or less
- the shear viscosity measured at a shear rate of 10 s ⁇ 1 is 800 mPa s or less
- the shear rate is 1,000 s ⁇
- E1 organic solvent
- [5] The aqueous coating composition according to any one of [1] to [4], which is for coil coating.
- a water-based coating composition that is excellent in storage stability even if it is a one-pack type, and that can form a coating film with good workability such as bending and crack resistance and scratch resistance during processing. be done.
- the aqueous coating composition of the present disclosure contains a coating film-forming resin (A), a cross-linking agent (B), a sulfonic acid compound (C) and an amine compound (D).
- the coating film-forming resin (A) contains an acrylic resin (A1).
- the acrylic resin (A1) represents a polymer having units derived from a monomer having a (meth)acryloyl group, by polymerizing a monomer mixture containing a monomer having an ethylenically unsaturated bond can be prepared.
- (meth)acrylic acid represents acrylic acid or methacrylic acid.
- Examples of the monomer having an ethylenically unsaturated bond include unsaturated carboxylic acids such as (meth)acrylic acid, crotonic acid, isocrotonic acid, 2-propenoic acid, ethacrylic acid, propylacrylic acid and isopropylacrylic acid; maleic acid; , fumaric acid, itaconic acid (including their anhydrides); unsaturated polycarboxylic acids such as ethyl maleate, butyl maleate, ethyl fumarate, butyl fumarate, ethyl itaconate, butyl itaconate Carboxylic acid monoalkyl ester; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t (meth)acrylate -butyl, n-pentyl (meth)acryl
- (meth) acrylonitrile monomer carboxylic acid vinyl ester such as vinyl acetate and vinyl propionate; styrene, ⁇ -methylstyrene, ⁇ -methylstyrene dimer, vinyl toluene, divinylbenzene and other styrene monomers; monomers; crosslinkable monomers such as polyfunctional vinyl monomers other than those described above; and the like. Only one kind of the monomer having an ethylenically unsaturated bond may be used, or two or more kinds thereof may be used in combination.
- the acrylic resin (A1) has a hydroxyl group. Since the acrylic resin (A1) has a hydroxyl group, the coating film can be cured by a cross-linking reaction between the hydroxyl group and the reactive group of the cross-linking agent. In order for the acrylic resin (A1) to obtain a hydroxyl group, a (meth)acrylic acid ester having a hydroxyl group may be used as the monomer having an ethylenically unsaturated bond when forming a polymer.
- the hydroxyl value of the acrylic resin (A1) having a hydroxyl group is preferably 5 mgKOH/g or more, more preferably 7 mgKOH/g or more, still more preferably 10 mgKOH/g or more, and more preferably 50 mgKOH/g or less. is 35 mgKOH/g or less, more preferably 30 mgKOH/g or less, still more preferably 25 mgKOH/g or less.
- the number of carbon atoms in the group bonded to the (meth)acryloyl group is preferably 1 to 3, more preferably 2.
- a (meth)acrylic acid ester having a hydroxyl group and having 1 to 3 carbon atoms in the group bonded to the (meth)acryloyl group there is an advantage that a coating film having excellent scratch resistance can be obtained.
- the content of the (meth)acrylic ester having a hydroxyl group and having 1 to 3 carbon atoms in the group bonded to the (meth)acryloyl group is preferably 70 mass in the (meth)acrylic ester having a hydroxyl group. % or more, more preferably 80 mass % or more, and the upper limit is 100 mass %.
- the weight average molecular weight of the acrylic resin (A1) is, for example, 50,000 or more, preferably 100,000 or more, more preferably 150,000 or more, and for example 10,000,000 or less, preferably 2,000,000. It is below. The greater the weight average molecular weight of the acrylic resin (A1), the better the scratch resistance and the advantage that a coating film with excellent workability can be obtained.
- the weight average molecular weight is a value converted to polystyrene by gel permeation chromatography (GPC).
- the acrylic resin (A1) preferably has an acid group. Since the acrylic resin (A1) has an acid group, dispersibility in an aqueous medium (E), which will be described later, can be imparted.
- the monomer having the ethylenically unsaturated bond may be an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid, or an unsaturated polycarboxylic acid.
- a monomer having an acid group such as a monoalkyl ester of an acid, a monomer having a sulfonic acid group, or a monomer having a phosphoric acid group may be used.
- the monomer having an acid group is preferably an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid, or a monoalkyl ester of an unsaturated polycarboxylic acid, more preferably an unsaturated monocarboxylic acid or an unsaturated polycarboxylic acid.
- Unsaturated monocarboxylic acids are more preferred, and (meth)acrylic acid is particularly preferred.
- the acid value of the acrylic resin (A1) is preferably 5 mgKOH/g or more, preferably 50 mgKOH/g or less, more preferably 30 mgKOH/g or less. Within the above range, there is an advantage that the acrylic resin (A1) can be stably dispersed in the aqueous medium (E).
- the acid value and hydroxyl value of the acrylic resin (A1) represent solid content acid value and solid content hydroxyl value, respectively, and can be measured according to JIS K 0070:1999.
- the glass transition temperature (Tg) of the acrylic resin (A1) is preferably ⁇ 70° C. or higher, more preferably 0° C. or higher, still more preferably 10° C. or higher, still more preferably 15° C. or higher, and preferably 95° C. or lower. , more preferably 90° C. or lower, still more preferably 85° C. or lower, and still more preferably 80° C. or lower.
- the glass transition temperature is obtained by dividing the mass fraction of each monomer constituting the acrylic resin (A1) by the Tg (K: Kelvin) value of the homopolymer derived from each monomer. can be calculated as the reciprocal of the sum of the quotients of More specifically, in the present specification, the glass transition temperature (Tg) is calculated by Fox's formula (TG Fox; Bull. Am. Phys. Soc., 1(3), 123 (1956)). can do.
- the resin is a polymer of a plurality of monomers (monomer A, monomer B, . . .
- Tga glass transition temperature (K) of homopolymer of monomer A
- wa mass fraction of monomer A
- Tgb glass transition temperature (K) of homopolymer of monomer B
- wb mass fraction of monomer B
- Tgn glass transition temperature (K) of homopolymer of monomer N
- wn mass fraction of monomer N
- the monomer having an ethylenically unsaturated bond preferably contains a (meth)acrylic acid alkyl ester, and the alkyl group has 1 to 6 carbon atoms, More preferably, it contains 1 to 4 (meth)acrylic acid alkyl esters.
- the content of the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 6 carbon atoms is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably It is 40% by mass or more, preferably 95% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.
- the content of the styrene-based monomer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass. %, and the lower limit is 0% by mass.
- the aqueous coating composition may contain a basic compound.
- a basic compound By including a basic compound in the water-based coating composition, some or all of the acid groups are neutralized, and good water-dispersibility can be imparted to the acrylic resin.
- the basic compound examples include ammonia, amine compounds, alkali metals, and the like.
- part of the amine compound (D) described later can be the basic compound.
- a known anionic and/or nonionic surfactant may be used to impart water dispersibility to the acrylic resin.
- the content of the acrylic resin (A1) in the coating film-forming resin (A) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, and the upper limit is 100% by mass. %.
- the acrylic resin (A1) is preferably an aqueous resin, and may be a water-soluble resin that is soluble in the aqueous medium (E), such as colloidal dispersion type, emulsion type (emulsion polymerization type, forced emulsion type). It may be a water-dispersible resin that can be dispersed in an aqueous medium (E) such as
- the acrylic resin (A1) is preferably a water-dispersible resin, more preferably an emulsion-type water-dispersible resin, and particularly preferably an emulsion-type water-dispersible resin produced by emulsion polymerization.
- the acrylic resin (A1) can be an aqueous resin by having an acid group and/or a hydroxyl group and/or by coexisting with an emulsifier.
- the average particle size of the emulsion particles is preferably 500 nm or less, more preferably 300 nm or less, and still more preferably 200 nm or less, such as 10 nm or more and 30 nm. Above, it may be 50 nm or more. Within the above range, there is an advantage that the emulsion particles and the coating composition containing the emulsion particles have good storage stability.
- the average particle size is an average particle size determined by a dynamic light scattering method. can be measured.
- the minimum film-forming temperature (MFT) of the acrylic resin (A1) is preferably 50° C. or higher, more preferably 60° C. or higher, and still more preferably 70° C. or higher. may be within the above range, there is an advantage that the scratch resistance of the resulting coating film is improved and blocking between the coating films is suppressed.
- the minimum film-forming temperature means the minimum temperature at which a crack-free uniform film is formed when the emulsion-type water-dispersible resin is dried, and conforms to JIS K 6828-2:2003. can be measured by
- the emulsion may be an emulsion in which multilayer-structured particles consisting of a core portion and a shell portion are dispersed.
- the multilayer structure particles can be prepared, for example, by the method described in JP-A-2002-12816.
- the acrylic resin (A1) can be produced by polymerizing a monomer having an ethylenically unsaturated bond. It can be carried out by heating under stirring in part or all of medium (E).
- the polymerization reaction is preferably an emulsion polymerization reaction. During the polymerization reaction, it is preferable to coexist with a polymerization initiator, and if necessary, it is preferable to coexist with an emulsifier.
- the reaction temperature is, for example, preferably 30 to 100° C., and the reaction time is preferably, for example, 1 to 10 hours.
- a radical polymerization initiator is preferable as the polymerization initiator.
- Persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate can be used as water-soluble free radical polymerization initiators.
- a redox initiator obtained by combining an oxidizing agent such as potassium persulfate, sodium persulfate, ammonium persulfate and hydrogen peroxide with a reducing agent such as sodium hydrogen sulfite, sodium thiosulfate, Rongalite and ascorbic acid can also be used.
- These radical polymerization initiators may be dissolved in part or all of the aqueous medium (E) and used as an aqueous solution.
- an anionic or nonionic emulsifier having a hydrophobic portion such as a hydrocarbon group having 6 or more carbon atoms and a hydrophilic portion such as a carboxylate, sulfonate or sulfate partial ester in the same molecule.
- system emulsifiers can be used.
- the anionic emulsifier include alkali metal salts or ammonium salts of sulfuric acid half esters of alkylphenols or higher alcohols; alkali metal salts or ammonium salts of alkyl or allylsulfonates; polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers.
- alkali metal salt or ammonium salt of sulfuric acid half-ester of polyoxyethylene allyl ether various anions having groups such as acrylic, methacrylic, propenyl, allyl, allyl ether, and maleic acid groups and ethylenically unsaturated bonds and system-reactive emulsifiers.
- nonionic emulsifiers include polyoxyalkylene ethers such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether and polyoxyethylene allyl ether; acrylic, methacrylic, propenyl, allyl, allyl ether, Examples include nonionic reactive emulsifiers having a group such as maleic acid and an ethylenically unsaturated bond.
- an auxiliary agent for adjusting the molecular weight such as a mercaptan compound or lower alcohol is effective from the viewpoint of promoting polymerization (preferably emulsion polymerization). From the viewpoint of promoting smooth and uniform formation of the film and improving the adhesion to the object to be coated, this is often preferable and is carried out as appropriate depending on the situation.
- any emulsion polymerization method such as a normal one-stage continuous monomer uniform dropping method, a core-shell polymerization method that is a multi-stage monomer feed method, or a power feed polymerization method that continuously changes the composition of the monomer to be fed during polymerization. Legal can also be used.
- the acrylic resin (A1) may be used in the preparation of the aqueous coating composition as an aqueous solution or dispersion containing the acrylic resin (A1) and part of the aqueous medium (E) described later.
- the aqueous solution or dispersion may further contain the emulsifier.
- a commercially available product may be used as the acrylic resin (A1). Moreover, only 1 type may be used and 2 or more types may be used together.
- the coating film-forming resin (A) may contain other resins (A2) in addition to the acrylic resin (A1).
- the other resins (A2) include hydroxyl-free acrylic resins, urethane resins, vinyl acetate resins, fluorine resins, vinyl chloride resins, etc., and each of them is preferably an aqueous resin, and is a water-dispersible resin. is more preferred, and an emulsion-type water-dispersible resin is even more preferred.
- the other resin (A2) may be used in the preparation of an aqueous coating composition as an aqueous solution or dispersion containing the other resin (A2) and part of the aqueous medium (E) in advance.
- the aqueous solution or dispersion may contain an emulsifier.
- the hydroxyl-free acrylic resin represents a polymer having a unit derived from a monomer having a (meth)acryloyl group, and among the monomers having an ethylenically unsaturated bond, a mixture of those having no hydroxyl group can be prepared by polymerizing
- the weight average molecular weight of the hydroxyl-free acrylic resin is preferably 50,000 or more, more preferably 100,000 or more, still more preferably 150,000 or more, and preferably 10,000,000 or less, more preferably 2,000,000 or less, more preferably 500,000 or less. Within the above range, there is an advantage that the workability of the resulting coating film is improved.
- the glass transition temperature of the hydroxyl group-free acrylic resin is preferably 80° C. or lower, more preferably 60° C. or lower, still more preferably 50° C. or lower, preferably 20° C. or higher, more preferably 30° C. or higher, and still more preferably. is above 40°C. Within the above range, there is an advantage that the scratch resistance is improved.
- the minimum film-forming temperature (MFT) of the acrylic resin is preferably 50° C. or higher, more preferably 60° C. or higher, and still more preferably 70° C. or higher, for example 200° C. or lower, 150° C. or lower, or 120° C. or lower. good too.
- MFT minimum film-forming temperature
- the hydroxyl-free acrylic resin preferably has an acid group.
- the acid value of the hydroxyl group-free acrylic resin is preferably 5 mgKOH/g or more, preferably 50 mgKOH/g or less, and more preferably 30 mgKOH/g or less.
- the hydroxyl-free acrylic resin When the hydroxyl-free acrylic resin is included, its content is preferably 20% by mass or more, more preferably 30% by mass or more, in the total of the acrylic resin (A1) and the hydroxyl-free acrylic resin. , preferably 90% by mass or less, more preferably 85% by mass or less.
- the hydroxyl value of the coating film-forming resin (A) is 5 mgKOH/g or more, preferably 7 mgKOH/g or more, more preferably 10 mgKOH/g or more, and 35 mgKOH/g or less, preferably 30 mgKOH/g or less. , more preferably 25 mgKOH/g or less.
- the acid value of the coating film-forming resin (A) is preferably 5 mgKOH/g or more, preferably 50 mgKOH/g or less, more preferably 30 mgKOH/g or less. Within this range, there is an advantage that the coating film-forming resin (A) can be stably dispersed in the aqueous medium (E).
- the weight average molecular weight of the coating film-forming resin (A) is, for example, 50,000 or more, preferably 100,000 or more, more preferably 150,000 or more, and for example, 10,000,000 or less, preferably 2,000. , 000 or less. By being within the above range, there is an advantage that a coating film having good workability can be obtained.
- the glass transition temperature (Tg) of the coating film-forming resin (A) is preferably ⁇ 70° C. or higher, more preferably 20° C. or higher, still more preferably 25° C. or higher, still more preferably 30° C. or higher, preferably 95 °C or lower, more preferably 70 °C or lower, still more preferably 60 °C or lower, and even more preferably 50 °C or lower.
- each parameter of the coating film-forming resin (A), except for the glass transition temperature is calculated as a weighted average based on the parameters and content of each resin. You may The glass transition temperature may also be calculated as the reciprocal of the sum of the values obtained by dividing the mass-based content of each coating film-forming resin by the glass transition temperature (K: Kelvin value).
- the content of the coating film-forming resin (A) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 80 parts by mass or more in 100 parts by mass of the solid content of the aqueous coating composition. , preferably 100 parts by mass or less, more preferably 95 parts by mass or less, and still more preferably 90 parts by mass or less.
- the content of the coating film-forming resin (A) represents the content of only the solid content.
- the solid content of the water-based coating composition represents the portion excluding the aqueous medium (E) from the entire water-based coating composition.
- the cross-linking agent (B) is a compound having two or more groups in one molecule capable of reacting with hydroxyl groups contained in the coating film-forming resin (A), and cross-links with the coating film-forming resin (A).
- a coating film can be formed.
- the cross-linking agent (B) contains an amino resin, and examples of the amino resin include melamine resin, urea resin and benzoguanamine.
- the amino resin preferably contains a melamine resin from the viewpoint of the storage stability of the resulting coating composition and the physical properties of the resulting coating film (processability, scratch resistance).
- Melamine resin is a thermosetting resin synthesized from melamine and aldehyde, and is a compound having three reactive functional groups represented by the following formula as reactive functional groups in one molecule of triazine nucleus, or Polycondensates are preferred.
- -NX 1 X 2 [X 1 and X 2 each independently represent a hydrogen atom, a methylol group or —CH 2 —OR 1 ; R 1 represents an alkyl group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 8 carbon atoms. When multiple —CH 2 —OR 1 are contained in the same molecule, multiple R 1 may be the same or different. ]
- R 1 is preferably an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, n-butyl group or isobutyl group.
- both X 1 and X 2 include a compound in which —CH 2 —OR 1 or a fullalkyl melamine resin (B1) which is a polycondensate thereof.
- a fullalkyl melamine resin (B1) which is a polycondensate thereof.
- resins include methylated melamine resins, butylated melamine resins, isobutylated melamine resins, and the like.
- the degree of polymerization in the fullalkyl-type melamine resin (B1) is 1 or more, preferably 1.2 or more, more preferably 1.5 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.
- the number average molecular weight of the fullalkyl-type melamine resin (B1) is preferably 300 or more, preferably 2,000 or less, more preferably 1,300 or less, still more preferably 1,000 or less, and particularly preferably 800 or less. is.
- the number average molecular weight is a value converted to polystyrene by gel permeation chromatography (GPC).
- fullalkyl melamine resin (B1) commercially available products can be used.
- Cymel 202, Cymel 235, Cymel 254, Cymel 1123, Cymel 1128, Cymel 1170, Mycoat 212 all methyl-butylated mixed melamine resins, manufactured by Allnex Japan
- Sumimar M-40S methylated melamine resin , Sumitomo Chemical
- Amidia J-820-60, Amidia L-127-60 both butylated melamine resins, manufactured by DIC).
- the content of the full-alkyl melamine resin (B1) in the cross-linking agent (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, and the upper limit is 100%. % by mass.
- the cross-linking agent (B) may contain another cross-linking agent (B2) in addition to the full-alkyl melamine resin (B1).
- the other crosslinking agent (B2) include amino resins such as melamine resins other than the fullalkyl-type melamine resin (B1), urea resins, and benzoguanamine resins.
- the amino resin has high reactivity with the coating film-forming resin (A), and the resulting coating film has good appearance and moisture resistance.
- cross-linking agent (B) only one type may be used, or two or more types may be used in combination.
- the content ratio of the cross-linking agent (B) to the content of the coating film-forming resin (A) ((B)/(A)) is preferably 5/95, more preferably 10/90 or more on a mass basis. , preferably 30/70 or less, more preferably 20/80 or less. Within the above range, there is an advantage that the workability and scratch resistance of the resulting coating film are improved.
- the sulfonic acid compound (C) can act as a catalyst that promotes the reaction between the film-forming resin (A) and the cross-linking agent (B). Therefore, there is an advantage that high reactivity can be imparted to the resulting coating composition.
- the sulfonic acid compound (C) may be a monosulfonic acid compound or a polysulfonic acid compound.
- the sulfonic acid compound include aliphatic sulfonic acids such as methanesulfonic acid; aromatic sulfonic acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and dinonylnaphthalenedisulfonic acid; be done.
- As said sulfonic acid compound (C) only 1 type may be used and 2 or more types may be used together.
- the content of the sulfonic acid compound (C) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the coating film-forming resin (A). It is 5 parts by mass or less, more preferably 3 parts by mass or less. When the content of the sulfonic acid compound (C) is within the above range, it is possible to form a coating film having good workability (adhesion, crack resistance) and scratch resistance on a precoated steel sheet.
- the amine compound (D) has the action of neutralizing the sulfonic acid compound (C), and by coexisting with the sulfonic acid compound (C) so as to achieve a specific neutralization rate, the water-based coating composition
- a specific neutralization rate the water-based coating composition
- the amine compound (D) is a compound having one or more amino groups, and is preferably a secondary or tertiary amine compound.
- the substituent of the nitrogen atom of the amine compound is preferably a saturated or unsaturated aliphatic hydrocarbon group, and the hydrogen atoms contained in the saturated or unsaturated aliphatic hydrocarbon group are each independently , —COOH, —OH, etc., and —CH 2 — contained in the saturated or unsaturated aliphatic hydrocarbon group may be replaced with —O—. Also, the substituents of the nitrogen atom of the amine compound may be bonded to each other to form a ring containing the nitrogen atom.
- Examples of the amine compound (D) include diethylamine, di-n-propylamine, diisopropylamine, diisobutylamine, di-n-butylamine, di-sec-butylamine, diamylamine, N-ethyl-1,2-dimethylpropyl
- Secondary aliphatic amine compounds such as amines, N-methylhexylamine, di-n-octylamine, and diallylamine; triethylamine, tributylamine, triallylamine, N,N-dimethylethanolamine, N-methyldiallylamine, N,N - tertiary aliphatic amine compounds such as dimethylallylamine; piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, etc. secondary cyclic amine compounds; N-methylpiperidine, N-methylpipe
- the boiling point of the amine compound (D) is preferably 50°C or higher, more preferably 70°C or higher, still more preferably 100°C or higher, and preferably 250°C or lower, more preferably 220°C or lower.
- the content of the amine compound (D) is such that the neutralization rate of the sulfonic acid compound (C) by the amine compound (D), that is, the neutralization rate in terms of moles calculated by the following formula is 100% or more. , 1,300% or less.
- Neutralization rate (%) [(base valence of amine compound (D) x number of moles of amine compound (D))/(acid number of sulfonic acid compound (C) x number of moles of sulfonic acid compound (C) )] ⁇ 100
- the neutralization rate is preferably 200% or more, more preferably 300% or more, and may be, for example, 1,300% or less, 1,100% or less, 1,000% or less, 900% or less, 800% or less. may be Although it should not be interpreted as being limited to a particular theory, within the above range, during storage (for example, 15 to 30 ° C.), the amine compound (D) is the sulfonic acid compound (C). By blocking the sulfonic acid group and suppressing the catalytic action, the storage stability can be improved. It is believed that the acid compound (C) can function as a catalyst.
- the full alkyl-type melamine resin (B1) is known to have lower reactivity than melamine resins generally used as cross-linking agents such as imino group-type melamine resins and methylol group-type melamine resins.
- the reactivity of the fullalkyl-type melamine resin (B1) is low in the case of low-temperature reaction (for example, 60 to 80° C.), and that the fullalkyl-type melamine resin It has been found that when (B1), the sulfonic acid compound (C) and the amine compound (D) are used in such a manner as to achieve the above-described neutralization rate, the reactivity at high temperatures increases. rice field.
- the storage stability is good, and it is suitable for high temperature and short time painting.
- a particularly suitable water-based coating composition can be obtained, and the crosslinking density can be increased, so there is an advantage that a coating film having excellent coating film processability (adhesion, crack resistance) can be obtained.
- the sulfonic acid compound (C) and the amine compound (D) may be used directly for the preparation of the water-based coating composition, or may be used as a mixture of them in advance for the preparation of the water-based coating composition.
- the sulfonic acid compound (C) and part or all of the amine compound (D) are a salt (for example, an amino group contained in the amine compound (D), and the sulfonic acid compound ( A salt in which the sulfonic acid group contained in C) is blocked) may be formed, and after forming a salt of the sulfonic acid compound (C) and part or all of the amine compound (D), the paint It may be incorporated into the composition.
- Salts of the sulfonic acid compound (C) and part or all of the amine compound (D) include aliphatic sulfonic acids such as methanesulfonic acid; aromatic sulfones such as dinonylnaphthalenedisulfonic acid and dinonylnaphthalenesulfonic acid. Acids and amine-blocked products thereof can be mentioned. Commercially available products can also be used as the salt of the sulfonic acid compound (C) and part or all of the amine compound (D).
- the content of the sulfonic acid compound (C) is 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the coating film-forming resin (A), and the neutralization rate is 100% or more. It is preferably 1,300% or less; the content of the sulfonic acid compound (C) is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the coating film-forming resin (A), and More preferably, the neutralization rate is 200% or more and 1,000% or less; the content of the sulfonic acid compound (C) is 2 parts by mass or more and 9 parts by mass with respect to 100 parts by mass of the coating film-forming resin (A).
- the neutralization rate is more preferably 300% or more and 900% or less. Since the coating composition has the amount and neutralization rate of the sulfonic acid compound (C) and the amine compound (D) as described above, the storage stability at low temperatures (storage temperature, for example, 15 to 30 ° C.) is high. In addition, the reactivity at high temperatures becomes higher, and the workability (adhesion, crack resistance) and scratch resistance of the resulting coating film become better.
- the total content of the coating film-forming resin (A), the cross-linking agent (B), the sulfonic acid compound (C) and the amine compound (D) in the solid content of the aqueous coating composition is, for example, preferably 50% by mass. Above, it is more preferably 70% by mass or more, still more preferably 80% by mass or more, and the upper limit is 100% by mass or less.
- the aqueous coating composition contains an aqueous medium (E).
- the aqueous medium (E) is preferably water, an organic solvent (E1), or a mixture of water and an organic solvent (E1).
- the organic solvent (E1) is preferably a hydrophilic organic solvent, and examples thereof include organic solvents having a solubility in water of 0.1 g/100 g H 2 O or more at 25°C.
- organic solvents include glycol-based solvents such as ethylene glycol, propylene glycol, butanediol, pentanediol, diethylene glycol, dipropylene glycol, and triethylene glycol; ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether, and diethylene glycol.
- Glycol ethers such as monobutyl ether acetate, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate solvent; alcohol solvents such as methanol, ethanol, isopropyl alcohol and benzyl alcohol; cyclic ether solvents such as dioxane and tetrahydrofuran; alcohol esters such as 2,2,4-trimethylpentane-1,3-diol monoisobutyrate ketone-based solvents such as acetone; and N-methyl-2-pyrrolidone.
- an organic solvent there is an advantage that the obtained coating composition has good wettability with the substrate.
- the boiling point of the organic solvent (E1) is preferably 150°C or higher, more preferably 180°C or higher, and preferably 300°C or lower, more preferably 250°C or lower.
- organic solvents include glycol solvents such as propylene glycol (1,2-propanediol), 1,4-butanediol, 1,5-pentanediol, diethylene glycol and dipropylene glycol. is particularly preferred. These may use only 1 type, and may use 2 or more types.
- the solubility of the organic solvent (E1) in water at 25° C. is preferably 0.1 g/100 g H 2 O or more, more preferably 1 g/100 g H 2 O or more, still more preferably 5 g/100 g H 2 O or more.
- the organic solvent (E1) may optionally be miscible with water.
- the content of the organic solvent (E1) in the aqueous medium (E) is 3% by mass or more, preferably 4% by mass or more, more preferably 5% by mass or more, preferably 30% by mass or less, and more It is preferably 20% by mass or less, more preferably 10% by mass or less.
- the content of the aqueous medium (E) is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less. , and more preferably 85% by mass or less.
- the water-based coating composition may contain an organic solvent other than the water-based medium (E), if necessary.
- organic solvents other than (E) include diethylene glycol dibutyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (texanol), and the like.
- the boiling point of the organic solvent other than (E) is preferably 150° C. or higher, more preferably 180° C. or higher, and preferably 300° C. or lower, more preferably 250° C. or lower.
- the water-based coating composition may further contain other additives, if necessary.
- the other additives include extender pigments; coloring agents such as coloring pigments and dyes; heat-shielding pigments; luster pigments; aggregates (resin particles, silica particles, etc.); agents (benzophenone-based ultraviolet absorbers, etc.); antioxidants (phenol-based, sulfide-based, hindered amine-based antioxidants, etc.); plasticizers; coupling agents (silane-based, titanium-based, zirconium-based coupling agents, etc.); Stopping agent; Viscosity modifier; Pigment dispersant; Pigment wetting agent; Surface modifier (silicone, organic polymer, etc.); Leveling agent; Antifreeze agents; emulsifiers; rust inhibitors; antiseptic agents; antifungal agents; These additives may be used alone or in combination of two or more.
- the viscosity modifier includes a hydrophilic associative viscosity modifier that forms a hydrogen bond between the viscosity modifiers or between the viscosity modifiers or the base resin and utilizes the bonding force (interaction), and a hydrophobic group (partially ), and examples of the associative viscosity modifier include an alkali-thickening viscosity modifier that utilizes the solubilization and thickening action of the polymer by alkali. can be mentioned.
- hydrophilic association-type viscosity modifier examples include polyamide-type viscosity modifiers.
- polyamide-type viscosity modifier a commercially available product may be used, for example (hereinafter, all are trade names), BYK-430, BYK-431 (manufactured by BYK-Chemie), Disparlon AQ-580, Disparlon AQ-600, Disparon AQ-607 (manufactured by Kusumoto Kasei Co., Ltd.), Tikuzol W-300, Tikuzol W-400LP (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.
- hydrophobic-associated viscosity modifier Commercially available products may be used as the hydrophobic-associated viscosity modifier. Co.), Primal RH-1020, Primal RM-2020 (manufactured by Dow Chemical Co.), SN Thickener 612, SN Thickener 621, Nopal 700N (manufactured by San Nopco) and the like.
- alkali-thickening viscosity modifier examples include viscose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, sodium polyacrylate, polyvinyl alcohol, and carboxymethyl cellulose.
- Commercially available products may also be used, for example, cellulose-based viscosity modifiers such as Tylose MH and Tylose H (manufactured by Merck); Primal ASE-60, Primal TT-615, Primal RM-5 (manufactured by Dow Chemical). , Uker polyfove (manufactured by Union Carbide Co.), and the like. These may use only 1 type and may use 2 or more types together.
- an associative viscosity modifier is preferred.
- the associative viscosity modifier By including the associative viscosity modifier, there is an advantage that coating workability with a roll coater (roll coater coatability) is improved.
- the viscosity of the coating composition can be made Newtonian at high shear rates. More preferably, it is used in combination with a hydrophobic associative viscosity modifier, which has the advantage of improving physical properties such as water resistance of the resulting coating film.
- the content of the viscosity modifier (F) contained in the aqueous coating composition of the present disclosure is 0.01 to 20 parts per 100 parts by mass of the total solid content of the coating film-forming resin (A) and the crosslinking agent (B). It is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass.
- amount of the viscosity modifier (F) is within such a range, there is an advantage that the coating workability with a roll coater (roll coater coatability) and the appearance and water resistance of the resulting coating film are improved. be.
- extender pigment examples include calcium carbonate, barium sulfate, clay, talc, mica, and glass fiber. These may use only 1 type and may use 2 or more types together.
- the amount of the extender is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 10 parts by mass, based on the total solid content of 100 parts by mass of the coating film-forming resin (A) and the curing agent (B). It is more than 30 parts by mass and less than 30 parts by mass. When the amount of the extender is within such a range, the scratch resistance of the coating film is likely to be improved.
- coloring pigment examples include colored inorganic pigments such as titanium dioxide, carbon black, graphite, iron oxide, and coal dust; Colored organic pigments such as throne yellow, isoindoline yellow, azo yellow, indathrone blue, dibromoanzathrone red, perylene red, azo red, anthraquinone red; aluminum powder, alumina powder, bronze powder, copper powder, tin powder, zinc powder , iron phosphide, and finely divided titanium. These may use only 1 type and may use 2 or more types together.
- colored inorganic pigments such as titanium dioxide, carbon black, graphite, iron oxide, and coal dust
- Colored organic pigments such as throne yellow, isoindoline yellow, azo yellow, indathrone blue, dibromoanzathrone red, perylene red, azo red, anthraquinone red
- the heat-shielding pigment does not absorb light in the near-infrared wavelength range (wavelength: 780 nm to 2,500 nm), or has a low absorption rate of light in the near-infrared wavelength range (wavelength: 780 nm to 2,500 nm). point to The heat-shielding pigment is not particularly limited, and the following inorganic heat-shielding pigments and organic heat-shielding pigments can be used.
- inorganic heat-shielding pigments include titanium oxide, magnesium oxide, barium oxide, calcium oxide, zinc oxide, zirconium oxide, yttrium oxide, indium oxide, sodium titanate, silicon oxide, nickel oxide, manganese oxide, chromium oxide, Metal oxide pigments such as iron oxide, copper oxide, cerium oxide, and aluminum oxide; Co., Ltd. Black 6350), iron oxide-cobalt oxide-chromium oxide (for example, Dainichiseika Co., Ltd.
- metal pigments such as silicon, aluminum, iron, magnesium, manganese, nickel, titanium, chromium, and calcium; and alloy pigments such as iron-chromium, bismuth-manganese, iron-manganese, and manganese-yttrium. . These may use only 1 type and may use 2 or more types together.
- organic thermal barrier pigments examples include azo pigments, azomethine pigments, lake pigments, thioindigo pigments, anthraquinone pigments (anthanthrone pigments, diaminoanthraquinonyl pigments, indanthrone pigments, flavanthrone pigments, anthraquinone pigments). pyrimidine pigments, etc.), perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, phthalocyanine pigments, quiniphthalone pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, and the like. be done. These may use only 1 type and may use 2 or more types together.
- the luster pigment examples include aluminum foil, bronze foil, tin foil, gold foil, silver foil, titanium metal foil, stainless steel foil, alloy foil such as nickel and copper, and foil pigments such as foil-like phthalocyanine blue. can. These may use only 1 type and may use 2 or more types together.
- waxes known to those skilled in the art for paints can be used, such as microcrystalline, polyethylene, polypropylene, paraffin, carnauba and modified products thereof. These may use only 1 type and may use 2 or more types together.
- the shear viscosity of the aqueous coating composition is preferably 30,000 mPa s or less, more preferably 20,000 mPa s or less, still more preferably 10 when measured at a temperature of 23° C. and a shear rate of 0.01 s ⁇ 1 ,000 mPa ⁇ s or less, preferably 3,000 mPa ⁇ s or more, more preferably 4,000 mPa ⁇ s or more, and still more preferably 5,000 mPa ⁇ s or more.
- the viscosity When measured at a shear rate of 10 s ⁇ 1 , it is preferably 800 mPa s or less, more preferably 700 mPa s or less, still more preferably 600 mPa s or less, preferably 300 mPa s or more, more preferably 400 mPa s or more, More preferably, it is 500 mPa ⁇ s or more.
- the viscosity When measured at a shear rate of 1,000 s ⁇ 1 , it is preferably 1,000 mPa ⁇ s or less, more preferably 150 mPa ⁇ s or more, and preferably 500 mPa ⁇ s or less.
- the viscosity When the viscosity is within the above range, the viscosity is suitable for picking up the paint during roll coater coating.
- the shear viscosity can be, for example, a value measured immediately after preparation of the coating composition.
- the shear viscosity can be measured using a rotational viscometer, for example, a stress-controlled rheometer MCR301 (manufactured by Anton Paar).
- the method for preparing the aqueous coating composition of the present disclosure is not particularly limited, and it can be prepared by mixing each component.
- it can be mixed using a roller mill, a ball mill, a bead mill, a pebble mill, a sand grind mill, a pot mill, a paint shaker or a disperser, a mixer, a kneader, or the like.
- a coating film formed from the aqueous coating composition and a method for producing the coating film are also included in the technical scope of the present disclosure.
- Examples of the object to be coated (substrate) to be coated with the water-based coating composition of the present disclosure include galvanized steel sheets, zinc-aluminum alloy coated steel sheets, and aluminum alloy coated steel sheets produced by a fusion method or an electrolytic method. , hot-dip zinc-aluminum-magnesium alloy plated steel sheet, stainless steel sheet, cold-rolled steel sheet, and the like. In addition to these steel sheets or plated steel sheets, metal sheets such as aluminum sheets (including aluminum alloy sheets) can also be applied.
- the object to be coated is preferably surface-treated.
- the object to be coated is preferably subjected to pretreatment such as alkali degreasing treatment, hot water washing treatment and water washing treatment, and then to chemical conversion treatment.
- the chemical conversion treatment may be performed by a known method, and includes, for example, chromate treatment, non-chromate treatment such as zinc phosphate treatment, and the like.
- the surface treatment can be appropriately selected according to the steel sheet to be used, but a treatment that does not contain heavy metals is preferable.
- the film thickness of the undercoat film is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
- the method for producing a coating film of the present disclosure includes: A step of applying the aqueous coating composition of the present disclosure to an object to be coated to form a coating film, and the coating film having a maximum temperature of 180 ° C. or higher and a drying and / or curing time of 120 seconds or less. drying and/or curing under conditions to form a coating film.
- the method for applying the water-based coating composition of the present disclosure to an object to be coated is not particularly limited, but employs a conventionally known method such as a roll coater method, an airless spray method, an electrostatic spray method, or a curtain flow coater method.
- a roll coater method and a curtain flow coater method are preferred, and a roll coater method is more preferred.
- the maximum temperature reached is preferably 200 seconds or more, and may be, for example, 280 seconds or less, 270 seconds or less, or 250 seconds or less.
- the drying and/or curing time is 120 seconds or less, can be 60 seconds or less, 30 seconds or less, 10 seconds or less, 6 seconds or less, preferably 1 second or more.
- the method for drying and/or curing the coating film is not particularly limited, but heating means such as hot air heating, infrared heating, and induction heating can be used.
- the film thickness (dry film thickness) of the coating film after drying and/or curing is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less.
- a laminate having the article to be coated and the coating film formed on the article to be coated is also included in the technical scope of the present disclosure.
- the article to be coated has the coating film on one side, it has a coating film formed from a known coating composition such as a coating composition containing an epoxy resin on the other side.
- the water-based coating composition of the present disclosure is usually used as coating conditions for metal substrates (for example, drying / curing temperature 60 to 80 ° C., drying / curing time 30 minutes to 1 hour). Even when the coating is performed under the condition of time, it is possible to obtain a coating film having high curability and good coating film physical properties (adhesion, workability such as crack resistance, and scratch resistance).
- the water-based coating composition of the present disclosure has high storage stability, and the coating film obtained is difficult to peel off from the coated object even during processing such as bending, and has good adhesion, and cracks do not occur.
- the crack resistance is suppressed, and the crack resistance is excellent, and the scratch resistance is also excellent. Therefore, the water-based coating composition of the present disclosure can be suitably used for coating metals, particularly precoating.
- a reaction vessel equipped with a thermometer, a condenser and a stirrer was charged with 40 parts by mass of ion-exchanged water and 0.4 parts by mass of Pelex SS-H and heated to 80°C under a nitrogen atmosphere. While maintaining the temperature at 80° C., the aqueous initiator solution was added dropwise over 180 minutes, and 10 minutes after the start of dropping, the monomer pre-emulsion was added dropwise from another port of the reaction vessel over 150 minutes to carry out emulsion polymerization. rice field. After the dropping of the aqueous initiator solution is completed, the mixture is further heated and stirred at 80° C. for 60 minutes, then cooled to room temperature, and 2.10 parts by mass of dimethylethanolamine is added thereto to form a coating film-forming resin (A-1). was dispersed in an aqueous medium (solid concentration: 45% by mass).
- Coating film-forming resins (A-2) to (A-11) were prepared in the same manner as described above, except that the monomer species, amount, and initiator amount were changed as shown in Table 1.
- Table 1 shows the special values such as the hydroxyl value of each coating film-forming resin.
- Coating film-forming resin (A) (A-12) Vylonal MD2000 (manufactured by Toyobo Co., Ltd., polyester resin emulsion); hydroxyl value: 6 mgKOH/g, acid value: 2 mgKOH/g, weight average molecular weight: 30,000, glass transition temperature: 67°C, lowest film-forming temperature : 48 ° C., average particle size: 125 nm, solid content concentration: 40% by mass Crosslinking agent (B) (B-1) Cymel 303 (manufactured by Allnex Japan Co., Ltd., full alkyl-type methylated melamine resin); Solid content concentration: 100% by mass Number average molecular weight: 455 (B-2) Cymel 300 (manufactured by Allnex Japan Co., Ltd., full alkyl-type methylated melamine resin); Solid content concentration: 100% by mass Number average molecular weight: 390 Other cross-linking
- Disperbyk190 manufactured by BYK Chemie
- Disperbyk190 1.63 parts by weight as a dispersant, 0.25 parts by weight of dimethylethanolamine, 0.05 parts by weight of SN-477T (manufactured by San Nopco) as an antifoaming agent, ion-exchanged water 32.9 parts by weight
- SN-477T manufactured by San Nopco
- ion-exchanged water 32.9 parts by weight
- Shear viscosity measurement The shear viscosity of the coating compositions obtained in Examples and Comparative Examples was measured using a stress-controlled rheometer MCR301 (manufactured by Anton Paar, jig: 50 mm parallel plate, gap: 0.5 mm). , shear viscosities at shear rates of 0.1 s ⁇ 1 , 10 s ⁇ 1 and 1,000 s ⁇ 1 were measured. The measurement temperature was 23°C.
- the coating composition adjusted to the initial viscosity (60 ⁇ 10 seconds (25° C.)) was placed in a 1 ⁇ 5 can for 8 to 9 minutes, sealed, and then allowed to stand in a constant temperature room at 40° C. Then, after 14 days (2 weeks), it was taken out and the viscosity was measured in the same manner as described above (viscosity over time (seconds)).
- the change rate of viscosity over time with respect to initial viscosity was calculated by the following formula, and storage stability was evaluated according to the following criteria. ⁇ or more was defined as a pass.
- Viscosity change rate (%) viscosity over time (seconds) / initial viscosity (seconds) x 100
- Object to be coated 300 mm ⁇ 2,000 mm ⁇ 0.35 mm size GL steel plate (manufactured by Nippon Steel Plate Co., Ltd.)
- ⁇ Painting conditions ⁇ Line speed: 50m/min
- Roll peripheral speed Application roll: 65 m/min (130% line speed ratio)
- Pickup roll 20 m/min (40% line speed ratio)
- ⁇ Backup roll pressure 60 kgf
- ⁇ Standard coating amount The mass of the dry coating film is 28 g / m 2 ⁇ Baking conditions: 30 seconds under conditions where the maximum temperature of the material to be coated is 230 ° C.
- the entire surface can be uniformly coated with the standard coating amount ⁇ : The entire surface can be uniformly coated, but the coating amount is 20 to 28 g / m It is 2 ⁇ : The entire surface can be coated, but the coating amount is less than 20 g / m 2 and the film thickness is uneven ⁇ : Uncoated parts occur and the entire surface cannot be coated
- the paint is picked up by the pickup roll, transferred to the application roll, transferred to the backup roll, and applied to the object to be coated.
- the pick-up roll properly picks up the paint
- the application roll and backup roll pressure properly transfer the paint to the backup roll. If only a small amount is wound up, unevenness occurs during transfer between rolls and the substrate is not uniformly coated.
- the appearance of the portion peeled off with the tape was evaluated according to the following criteria. A score of 4 or more was regarded as passing. 5: No metal substrate is observed in the portion where the tape has been peeled off. 4: A metal base portion is observed in less than 20% (more than 0%) of the area of the tape-peeled portion. 3: A metal base portion is observed in 20% or more and less than 50% of the area of the tape-peeled portion. 2: A metal base portion is observed in 50% or more and less than 80% of the area of the tape-peeled portion. 1: A metal base portion is observed in 80% or more of the area of the tape-peeled portion.
- the base material is not exposed even if the load exceeds 3,000 g ⁇ : The load exceeds 2,000 and is 3,000 g or less ⁇ : The load exceeds 1,000 g and 2,000 g or less ⁇ : The load is 1,000 g or less
- Examples 1 to 45 are examples of the present disclosure, and had high storage stability, excellent processability, and good scratch resistance.
- Comparative Examples 1 and 2 are examples in which the acrylic resin (A1) had a hydroxyl value of less than 5 mgKOH/g, and were inferior in scratch resistance.
- Comparative Examples 3 and 4 are examples in which the hydroxyl value of the acrylic resin (A1) exceeds 35 mgKOH/g, and were inferior in storage stability and workability.
- Comparative Examples 5 and 6 were examples in which the rate of neutralization of the sulfonic acid compound (C) by the amine compound (D) was less than 100%, and the storage stability was poor.
- Comparative Example 7 was an example in which the rate of neutralization of the sulfonic acid compound (D) by the amine compound (D) exceeded 1,300%, and the storage stability was poor.
- Comparative Examples 8 and 9 are examples in which the fullalkyl-type melamine resin (B1) was not included as the cross-linking agent (B), and were inferior in workability.
- Comparative Example 10 is an example using a phosphoric acid compound without containing the sulfonic acid compound (C), and was inferior in storage stability and scratch resistance.
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Abstract
Description
[1]
塗膜形成樹脂(A)、架橋剤(B)、スルホン酸化合物(C)及びアミン化合物(D)を含む水性塗料組成物であって、
前記塗膜形成樹脂(A)が、アクリル樹脂(A1)を含むものであり、
前記塗膜形成樹脂(A)の水酸基価が、5mgKOH/g以上35mgKOH/g以下であり、
前記架橋剤(B)が、フルアルキル型メラミン樹脂(B1)を含むものであり、
前記アミン化合物(D)による、前記スルホン酸化合物(C)の酸基のモル換算の中和率が、100%以上1,300%以下である、水性塗料組成物。
[2]前記塗膜形成樹脂(A)の重量平均分子量が、100,000以上である[1]に記載の水性塗料組成物。
[3]温度23℃において、剪断速度0.01s-1で測定した剪断粘度が30,000mPa・s以下、剪断速度10s-1で測定した剪断粘度が800mPa・s以下、剪断速度1,000s-1で測定した剪断粘度が150mPa・s以上である[1]又は[2]に記載の水性塗料組成物。
[4]更に、有機溶剤(E1)を含む、[1]~[3]のいずれか1つに記載の水性塗料組成物。
[5]コイルコーティング用である、[1]~[4]のいずれか1つに記載の水性塗料組成物。
[6][1]~[5]のいずれか1つに記載の水性塗料組成物を被塗物に塗工して、塗装膜を形成する工程、及び
前記塗装膜を、最高到達温度が180℃以上であり、乾燥及び/又は硬化時間が120秒以下である条件下で、乾燥及び/又は硬化させて塗膜とする工程を含む、塗膜の製造方法。
前記塗膜形成樹脂(A)は、アクリル樹脂(A1)を含む。前記アクリル樹脂(A1)は、(メタ)アクリロイル基を有する単量体に由来する単位を有する重合体を表し、エチレン性不飽和結合を有する単量体を含む単量体混合物を重合することによって調製することができる。なお本明細書において、(メタ)アクリル酸は、アクリル酸又はメタクリル酸を表す。
前記エチレン性不飽和結合を有する単量体は1種のみを用いてもよく、2種以上を併用してもよい。
前記アクリル樹脂(A1)が酸基を得るためには、重合体とする際、前記エチレン性不飽和結合を有する単量体として、不飽和モノカルボン酸、不飽和ポリカルボン酸、不飽和ポリカルボン酸のモノアルキルエステル、スルホン酸基を有する単量体、リン酸基を有する単量体等の酸基を有する単量体を用いればよい。
より詳細には、本明細書において、前記ガラス転移温度(Tg)は、Foxの式(T.G.Fox;Bull.Am.Phys.Soc.,1(3),123(1956))によって算出することができる。
例えば、樹脂が、複数のモノマー(モノマーA、モノマーB、…モノマーN)の重合体である場合、下記一般式:
1/Tg=wa/Tga+wb/Tgb+・・・+wn/Tgn
で表されるTgを樹脂のTgとする。
ここで、
Tga:モノマーAのホモポリマーのガラス転移温度(K)、wa:モノマーAの質量分率、
Tgb:モノマーBのホモポリマーのガラス転移温度(K)、wb:モノマーBの質量分率、
Tgn:モノマーNのホモポリマーのガラス転移温度(K)、wn:モノマーNの質量分率、
を意味し、
wa+wb+・・・+wn=1である。
また、公知のアニオン性及び/又はノニオン性界面活性剤を用いて、アクリル樹脂に対して水分散性を付与してもよい。
また非イオン系の乳化剤としては、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアリルエーテル等のポリオキシアルキレンエーテル;アクリル系、メタクリル系、プロペニル系、アリル系、アリルエーテル系、マレイン酸系等の基とエチレン性不飽和結合とを有するノニオン系反応性乳化剤等が挙げられる。
前記架橋剤(B)は、一分子中に前記塗膜形成樹脂(A)に含まれる水酸基と反応しうる基を2個以上有する化合物であり、前記塗膜形成樹脂(A)と架橋反応し塗膜を形成することができる。前記架橋剤(B)はアミノ樹脂を含み、前記アミノ樹脂としては、メラミン樹脂、尿素樹脂及びベンゾグアナミン等を挙げることができる。得られる塗料組成物の貯蔵安定性及び得られる塗膜の諸物性(加工性、耐傷付性)の観点からアミノ樹脂はメラミン樹脂を含むことが好ましい。
-NX1X2
[X1、X2は、それぞれ独立に、水素原子、メチロール基又は-CH2-OR1を表す。
R1は、炭素数1~8のアルキル基、好ましくは炭素数1~8の直鎖状又は分枝鎖状アルキル基を表す。
同一分子中に複数の-CH2-OR1が含まれる場合、複数のR1は、同一であっても異なっていてもよい。]
なお本明細書において、数平均分子量は、ゲル・パーミエーションクロマトグラフィ(GPC)によるポリスチレン換算した値である。
前記スルホン酸化合物(C)は、前記塗膜形成樹脂(A)と架橋剤(B)との反応を促進する触媒として作用しうる。そのため、得られる塗料組成物に高い反応性を付与できるという利点がある。
前記アミン化合物(D)は、スルホン酸化合物(C)を中和する作用を有しており、特定の中和率となるようスルホン酸化合物(C)と共存させることで、水性塗料組成物の貯蔵時(例えば15~50℃)の安定性と、塗装後の加熱乾燥・硬化時の高反応性とを両立できるという利点がある。前記アミン化合物(D)は、その一部が、スルホン酸化合物(C)と塩を形成して存在していてもよい。
中和率(%)=[(アミン化合物(D)の塩基価数×アミン化合物(D)のモル数)/(スルホン酸化合物(C)の酸価数×スルホン酸化合物(C)のモル数)]×100
前記水性塗料組成物は、水性媒体(E)を含む。前記水性媒体(E)は、水、有機溶剤(E1)又は水と有機溶剤(E1)との混合物であることが好ましい。
前記水性塗料組成物は、必要に応じて、更に、その他の添加剤を含んでいてもよい。前記その他の添加剤としては、例えば、体質顔料;着色顔料、染料等の着色剤;遮熱顔料;光輝性顔料;骨材(樹脂粒子、シリカ粒子等);ワックス;前記以外の溶剤;紫外線吸収剤(ベンゾフェノン系紫外線吸収剤等);酸化防止剤(フェノール系、スルフォイド系、ヒンダードアミン系酸化防止剤等);可塑剤;カップリング剤(シラン系、チタン系、ジルコニウム系カップリング剤等);タレ止め剤;粘性調整剤;顔料分散剤;顔料湿潤剤;表面調整剤(シリコーン系、有機高分子系等);レベリング剤;色分かれ防止剤;沈殿防止剤;沈降防止剤;消泡剤;界面活性剤;凍結防止剤;乳化剤;防錆剤;防腐剤;防かび剤;抗菌剤;安定剤等がある。これらの添加剤は、1種のみを用いてもよく、2種以上を併用してもよい。
これらは1種のみを用いてもよいし、2種以上を併用してもよい。
前記剪断粘度は、例えば、塗料組成物調製直後に測定した値とすることができる。
前記剪断粘度は、回転式粘度計を用いて測定でき、例えば、応力制御型レオメーターMCR301(アントンパール社製社製)等を用いて測定できる。
本開示の水性塗料組成物の調製方法は特に限定されず、各成分を混合することにより調製することができる。例えば、ローラーミル、ボールミル、ビーズミル、ペブルミル、サンドグラインドミル、ポットミル、ペイントシェーカー又はディスパー等の混合機分散機、混錬機等を用いて混合することができる。
本開示の水性塗料組成物の塗装の対象となる被塗物(基材)としては、例えば、溶融法又は電解法等により製造される亜鉛めっき鋼板、亜鉛-アルミニウム合金めっき鋼板、アルミニウム合金めっき鋼板、溶融亜鉛-アルミニウム-マグネシウム合金めっき鋼板、ステンレス鋼板、冷延鋼板等が挙げられる。また、これら鋼板又はめっき鋼板以外に、アルミニウム板(アルミニウム合金板を含む)等の金属板も塗装対象とすることができる。
本開示の塗膜の製造方法は、
被塗物に本開示の水性塗料組成物を塗装して塗装膜を形成する工程、及び
前記塗装膜を、最高到達温度が180℃以上であり、乾燥及び/又は硬化時間が120秒以下である条件下で、乾燥及び/又は硬化させて塗膜とする工程を含む。
ペレックスSS-H(界面活性剤、花王社製)0.6質量部を、イオン交換水60質量部に溶解させた。これに、メタクリル酸メチル53.0質量部、アクリル酸n-ブチル39.2質量部、メタクリル酸2-ヒドロキシエチル5.8質量部及びメタクリル酸2.0質量部から成るモノマー混合物を加えてかくはんし、モノマープレエマルション150.5質量部を調製した。別途、開始剤として過硫酸アンモニウム1.0質量部をイオン交換水20質量部に溶解して開始剤水溶液を調製した。
塗膜形成樹脂(A)
(A-12)バイロナールMD2000(東洋紡社製、ポリエステル樹脂エマルション);水酸基価:6mgKOH/g、酸価:2mgKOH/g、重量平均分子量:30,000、ガラス転移温度:67℃、最低造膜温度:48℃、平均粒子径:125nm、固形分濃度:40質量%
架橋剤(B)
(B-1)サイメル303(オルネクスジャパン社製、フルアルキル型メチル化メラミン樹脂);固形分濃度:100質量% 数平均分子量:455
(B-2)サイメル300(オルネクスジャパン社製、フルアルキル型メチル化メラミン樹脂);固形分濃度:100質量% 数平均分子量:390
その他の架橋剤
(b-1)サイメル327(オルネクスジャパン社製、イミノ基型メチル化メラミン樹脂);固形分濃度:90質量% 数平均分子量:470
(b-2)マイコート508(オルネクスジャパン社製、イミノ基型ブチル化メラミン樹脂):固形分濃度:80質量%、数平均分子量:1,500
スルホン酸化合物(C)
(C-1)AC400S(テイカ社製、ドデシルベンゼンスルホン酸);固形分濃度:25質量%
(C-2)AC700(テイカ社製、パラトルエンスルホン酸);固形分濃度:25質量%
(C-3)Nacure-1051(楠本化成社製、ジノニルナフタレンスルホン酸);固形分濃度:51質量%
その他の酸化合物
(c-1)Cycat296(オルネクスジャパン社製、リン酸化合物);固形分濃度:50質量%
アミン化合物(D)
(D-1)DMEA(ジメチルエタノールアミン、三菱瓦斯化学社製);沸点:134℃
(D-2)AMP(2-アミノ-2-メチル-1-プロパノール、国産化学社製);沸点:165℃
(D-3)TEA(トリエチルアミン、三菱瓦斯化学社製);沸点:90℃
水性媒体(E)
(E1-1)ジエチレングリコール(日本触媒社製);沸点:244℃、水への溶解度:無限大(水と任意に混和)
(E1-2)プロピレングリコール(三協化学社製);沸点:187℃、水への溶解度:無限大(水と任意に混和)
(E1-3)ジプロピレングリコール(昭和化学社製);沸点:232℃、水への溶解度:無限大(水と任意に混和)
(E1-4)1,4-ブタンジオール(三協化学社製);沸点:228℃、水への溶解度:無限大(水と任意に混和)
(E1-5)1,5-ペンタンジオール(宇部興産社製);沸点:242℃、水への溶解度:無限大(水と任意に混和)
粘性調整剤(F)
(F-1)SNシックナー612(ポリエーテルウレタン系疎水会合型粘性調整剤、サンノプコ社製);固形分濃度:40質量%
(F-2)SNシックナー621(ポリエーテルウレタン系疎水会合型粘性調整剤、サンノプコ社製);固形分濃度:30質量%
(F-3)アデカノールUH-526(ポリエーテルウレタン系疎水会合型粘性調整剤、ADEKA社製);固形分濃度:30質量%
(F-4)プライマルRM-2020NPR(ポリエーテルウレタン系疎水会合型粘性調整剤、ダウケミカル社製);固形分濃度:20質量%
(F-5)プライマルASE-60(ポリアクリル酸エステルエマルション系アルカリ膨潤型増粘剤、ダウケミカル社製);固形分濃度:28質量%
分散剤としてDisperbyk190(ビックケミー社製)1.63質量部、ジメチルエタノールアミン 0.25質量部、消泡剤としてSN-477T(サンノプコ社製)0.05質量部、イオン交換水 32.9質量部及び顔料として二酸化チタン(Ti-Pure R-706、DuPont社製)65.2質量部を予備混合した後、SGミル(分散媒体:ガラスビーズ)を用いて、1,600rpmで、顔料粗粒の最大粒子径が5μmになるまで分散し、顔料分散ペーストを得た。
前記製造例で得られた顔料分散ペースト55.1質量部、前記製造例で得られた塗膜形成樹脂(A-1)80.0質量部、塗膜形成樹脂(A-8)20.0質量部、架橋剤(B-1)としてサイメル303 17.6質量部を混合した後、水性媒体としてジエチレングリコール(E1-1)5.4質量部及びプロピレングリコール(E1-2)5.4質量部を混合、かくはんした。次に、スルホン酸化合物(C-1)としてドデシルベンゼンスルホン酸 1.2質量部及びアミン化合物(D-1)としてジメチルエタノールアミン 1.9質量部をディスパーでかくはんし、更に、粘性調整剤(F-1)としてシックナーSN-612 0.2質量部とをかくはんしながら混合し、塗料組成物1を得た。
各成分の種類及び量を、表2~7に記載のように変更したこと以外は、塗料組成物1と同様にして塗料組成物を調製した。
厚さ0.4mmの溶融亜鉛めっき鋼板をアルカリ脱脂した後、リン酸処理剤サーフコートEC2310(日本ペイント・サーフケミカルズ社製)を、鋼板表面及び裏面に塗布することにより、ノンクロム化成処理を施し、乾燥した。
次に、鋼板の表面に、製造例で得られた塗料組成物を1、乾燥塗膜が18μmとなるようにバーコーターを用いて塗装し、素材最高到達温度230℃となる条件で30秒間焼付けを行ない、表面塗膜を形成し、塗装鋼板を得た。
実施例及び比較例で得られた塗料組成物の剪断粘度を、応力制御型レオメーターMCR301(アントンパール社製、治具:50mmパラレルプレート、ギャップ:0.5mm)を用いて、剪断速度0.1s-1、10s-1及び1,000s-1での剪断粘度を測定した。測定温度は23℃とした。
JIS K 5600 2-2(フローカップ法)に規定する方法に準拠し、フォードカップNo.4(上島製作所社製)を用いて評価した。
実施例及び比較例で得られた塗料組成物にイオン交換水を添加し、粘度を60±10秒となるよう調整した(初期粘度(秒))。詳細には、初期粘度は、前記イオン交換水で希釈し、ディスパーを用いて1,000rpmで3分間かくはんした後、直ちに測定した粘度とした。塗料温度は25℃とした。
初期粘度に対する経時粘度の変化率を下記式により算出し、貯蔵安定性を下記基準により評価した。○以上を合格とした。
粘度変化率(%)=経時粘度(秒)/初期粘度(秒)×100
◎:粘度変化率が0%以上30%未満である。
○:粘度変化率が30%以上50%未満である。
△:粘度変化率が50%以上100%未満である。
×:粘度変化率が100%以上である。
実施例及び比較例で得られた塗料組成物について、3本のロール(バックアップロール、アプリケーションロール、ピックアップロール)を備えた小型テストコーター(エヌ・ケイ・テック社製)を用いて、以下の条件で被塗物に塗装し、ロールコーター塗工性を、下記基準に従って評価した。○以上を合格とした。なお、試験条件は、室温23℃、湿度60RH%とした。
・被塗物:300mm×2,000mm×0.35mmサイズのGL鋼板(日鉄鋼板社製)
・塗装条件:
・ラインスピード:50m/min
・ロール周速:アプリケーションロール:65m/min(対ラインスピード比130%)、ピックアップロール:20m/min(対ラインスピード比40%)
・バックアップロール圧:60kgf
・基準塗布量:乾燥塗膜の質量が28g/m2
・焼付け条件:被塗物の素材最高到達温度230℃となる条件で30秒間
◎:全面を基準塗布量で均一に塗布できる
○:全面を均一に塗布できるが、塗布量が20~28g/m2である
△:全面を塗布できるが、塗布量が20g/m2未満であり、膜厚が不均一となる
×:未塗装部が生じ、全面を塗装することが出来ない
実施例及び比較例で得られた各塗装鋼板を5cm×3cmに切断し、ハゼ折り機(上島製作所社製)を用いて、塗膜面が表側になるように予備曲げをした。その試験片に同一の厚み(0.4mm)の鋼板を2枚挟み、プレス機(協立工業社製)にて折り曲げ加工した。塗装鋼板の加工部にセロハンテープ(登録商標)(LP-24、ニチバン社製)を密着させ、一気に剥離し、加工部塗膜の密着性を評価した。テープで剥離した部分の外観を、下記基準により評価した。4点以上を合格とした。
5:テープ剥離の部分に金属の素地が認められない。
4:テープ剥離の部分の面積の(0%を超え)20%未満に金属の素地部が認められる。
3:テープ剥離の部分の面積の20%以上50%未満に金属の素地部が認められる。
2:テープ剥離の部分の面積の50%以上80%未満に金属の素地部が認められる。
1:テープ剥離の部分の面積の80%以上に金属の素地部が認められる。
実施例及び比較例で得られた各塗装鋼板を5cm×3cmに切断し、ハゼ折り機(上島製作所社製)を用いて、塗膜面が表側になるように予備曲げをした。その試験片に同一の厚み(0.4mm)の鋼板を5枚挟み、プレス機(協立工業社製)にて折り曲げ加工した。加工部分の塗膜の状態(クラック)を15倍ルーペで観察し、加工性を下記基準により評価した。4点以上を合格とした。なお、試験条件は、温度23℃、湿度60RH%とした。
5:加工部分にクラックが認められない。
4:加工部分の面積の(0%を超え)20%未満にクラックが認められる。
3:加工部分の面積の20%以上50%未満にクラックが認められる。
2:加工部分の面積の50%以上80%未満にクラックが認められる。
1:加工部分の面積の80%以上にクラックが認められる。
連続加重式引掻強度試験機TYPE:18/18L(新東科学社製)を用いて、実施例及び比較例で得られた各塗装鋼板の塗膜面にR0.4mmとなるようにR加工を施したダイヤモンド針(R加工を施した円錐状のスクラッチ針、直径0.4mm)をあて、荷重をかけて300mm/min、移動幅10cmで1回擦り付けた。塗膜面が傷付き、素地の露出が確認できたときの荷重の重さを下記基準により評価した。○以上を合格とした。なお、荷重は500gfずつかけ、試験条件は、温度23℃、湿度60RH%とした。
◎:荷重3,000gを超えても素地が露出しない
○:荷重2,000を超え3,000g以下
△:荷重1,000gを超え2,000g以下
×:荷重1,000g以下
Claims (6)
- 塗膜形成樹脂(A)、架橋剤(B)、スルホン酸化合物(C)及びアミン化合物(D)を含む水性塗料組成物であって、
前記塗膜形成樹脂(A)が、水酸基を有するアクリル樹脂(A1)を含むものであり、
前記塗膜形成樹脂(A)の水酸基価が、5mgKOH/g以上35mgKOH/g以下であり、
前記架橋剤(B)が、フルアルキル型メラミン樹脂(B1)を含むものであり、
前記アミン化合物(D)による、前記スルホン酸化合物(C)の酸基のモル換算の中和率が、100%以上1,300%以下である、水性塗料組成物。 - 前記塗膜形成樹脂(A1)の重量平均分子量が、100,000以上である請求項1に記載の水性塗料組成物。
- 温度23℃において、剪断速度0.01s-1で測定した剪断粘度が30,000mPa・s以下、剪断速度10s-1で測定した剪断粘度が800mPa・s以下、剪断速度1,000s-1で測定した剪断粘度が150mPa・s以上である請求項1又は2に記載の水性塗料組成物。
- 更に、有機溶剤(E1)を含む、請求項1~3のいずれか1項に記載の水性塗料組成物。
- コイルコーティング用である、請求項1~4のいずれか1項に記載の水性塗料組成物。
- 請求項1~5のいずれか1項に記載の水性塗料組成物を被塗物に塗工して、塗装膜を形成する工程、及び
前記塗装膜を、最高到達温度が180℃以上であり、乾燥及び/又は硬化時間が120秒以下である条件下で、乾燥及び/又は硬化させて塗膜とする工程を含む、塗膜の製造方法。
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JP2021097518A JP7101294B1 (ja) | 2021-06-10 | 2021-06-10 | 水性塗料組成物、塗膜及び塗膜の製造方法 |
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WO2022259774A1 true WO2022259774A1 (ja) | 2022-12-15 |
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JP (1) | JP7101294B1 (ja) |
KR (1) | KR20240018566A (ja) |
CN (1) | CN117440996A (ja) |
AU (1) | AU2022291046A1 (ja) |
TW (1) | TW202302673A (ja) |
WO (1) | WO2022259774A1 (ja) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03200884A (ja) * | 1989-10-11 | 1991-09-02 | Kansai Paint Co Ltd | 熱硬化性塗料組成物 |
JPH07179813A (ja) * | 1993-12-24 | 1995-07-18 | Nippon Paint Co Ltd | 水性コーティング組成物 |
JP2000017225A (ja) * | 1998-07-01 | 2000-01-18 | Mitsubishi Rayon Co Ltd | 金属被覆用水性塗料組成物 |
JP2001240624A (ja) * | 2000-02-29 | 2001-09-04 | Mitsubishi Rayon Co Ltd | アクリル系水溶性共重合体およびアクリル系水溶性塗料組成物 |
JP2001323207A (ja) * | 2000-05-18 | 2001-11-22 | Mitsubishi Rayon Co Ltd | 水性塗料組成物 |
JP2015174958A (ja) * | 2014-03-17 | 2015-10-05 | 日本ペイント・オートモーティブコーティングス株式会社 | 水性塗料組成物及び塗膜形成方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3200884B2 (ja) | 1991-09-30 | 2001-08-20 | 日本板硝子株式会社 | 厚ガラス板の割断方法 |
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2021
- 2021-06-10 JP JP2021097518A patent/JP7101294B1/ja active Active
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2022
- 2022-04-22 CN CN202280040929.XA patent/CN117440996A/zh active Pending
- 2022-04-22 KR KR1020247000004A patent/KR20240018566A/ko unknown
- 2022-04-22 WO PCT/JP2022/018535 patent/WO2022259774A1/ja active Application Filing
- 2022-04-22 AU AU2022291046A patent/AU2022291046A1/en active Pending
- 2022-05-05 TW TW111117024A patent/TW202302673A/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03200884A (ja) * | 1989-10-11 | 1991-09-02 | Kansai Paint Co Ltd | 熱硬化性塗料組成物 |
JPH07179813A (ja) * | 1993-12-24 | 1995-07-18 | Nippon Paint Co Ltd | 水性コーティング組成物 |
JP2000017225A (ja) * | 1998-07-01 | 2000-01-18 | Mitsubishi Rayon Co Ltd | 金属被覆用水性塗料組成物 |
JP2001240624A (ja) * | 2000-02-29 | 2001-09-04 | Mitsubishi Rayon Co Ltd | アクリル系水溶性共重合体およびアクリル系水溶性塗料組成物 |
JP2001323207A (ja) * | 2000-05-18 | 2001-11-22 | Mitsubishi Rayon Co Ltd | 水性塗料組成物 |
JP2015174958A (ja) * | 2014-03-17 | 2015-10-05 | 日本ペイント・オートモーティブコーティングス株式会社 | 水性塗料組成物及び塗膜形成方法 |
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JP2022189126A (ja) | 2022-12-22 |
JP7101294B1 (ja) | 2022-07-14 |
CN117440996A (zh) | 2024-01-23 |
AU2022291046A1 (en) | 2023-10-26 |
TW202302673A (zh) | 2023-01-16 |
KR20240018566A (ko) | 2024-02-13 |
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