JP2022189126A - Aqueous coating composition, coating film, method for producing coating film - Google Patents
Aqueous coating composition, coating film, method for producing coating film Download PDFInfo
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- JP2022189126A JP2022189126A JP2021097518A JP2021097518A JP2022189126A JP 2022189126 A JP2022189126 A JP 2022189126A JP 2021097518 A JP2021097518 A JP 2021097518A JP 2021097518 A JP2021097518 A JP 2021097518A JP 2022189126 A JP2022189126 A JP 2022189126A
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- coating film
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- coating composition
- resin
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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
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- 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
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- 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
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- 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
- 229920002647 polyamide Polymers 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
- 239000001993 wax Substances 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
Abstract
Description
本発明は、水性塗料組成物、塗膜及び塗膜の製造方法に関する。 TECHNICAL FIELD The present invention relates to an aqueous coating composition, a coating film, and a method for producing a coating film.
冷間圧延鋼板、めっき鋼板等の金属基材に塗装を施し、その後成形加工に供される塗装鋼板は、プレコート鋼板(以下、「PCM」ともいう)とも呼ばれ、シャッター、天戸、ドア、屋根及びサイディング等の建築部材;クーラー室外機等の電気機器類の外装材;内装材等の用途に用いられている。前記プレコート鋼板は、通常、前記金属基材の表面に塗料組成物を塗工し、例えば、200~270℃で30~60秒の加熱(焼付け)を行って塗膜を形成することで製造され、その後、成型加工に供される。このため、プレコート鋼板の塗膜には、加工の際、割れや剥がれが生じない程度の加工性や、傷や凹みが生じない程度の硬度が求められる。 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.
塗料組成物には、塗膜形成樹脂を含む主剤と、架橋剤を含む硬化剤とが同一の系内に共存している一液形塗料組成物と、主剤及び硬化剤を別々に保管し、使用時に混合して用いる二液形塗料組成物が存在する。このうち、二液形塗料組成物は、主剤と硬化剤とを使用直前まで混合しないため、一液形塗料組成物と比較すると貯蔵安定性は優位である。しかしながら、二液形塗料組成物では、使用時、主剤と硬化剤とを所定の割合で混合し、均一になるようかくはんする必要があることや、使用可能な時間に制限があること等、その取扱いや塗装作業性が問題となる場合があり、一液形塗料組成物が求められている。 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, There exists a two-component paint composition that is used by mixing at the time of use. Among them, 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. However, in a two-component coating composition, it is necessary to mix the main agent and the curing agent in a predetermined ratio before use, and it is necessary to stir the mixture to make it uniform. Handling and coating workability may become a problem, and a one-component coating composition is desired.
また、近年、環境負荷低減の意識が高まり、環境に配慮した商品への置換が求められている。塗料分野においても、例えば、揮発性有機化合物(VOC)の使用量を低減することが要求されており、水性塗料組成物を用いることにより、このような要求を満たすことができる。すなわち、市場においては、一液形の水性塗料組成物へのニーズが非常に高くなってきている。 Moreover, in recent years, there has been a growing awareness of the need to reduce the burden on the environment, and there has been a demand for replacement with environmentally friendly products. Also in the field of paints, for example, there is a demand to reduce the amount of volatile organic compounds (VOCs) used, and such a demand can be met by using a water-based paint composition. That is, in the market, the need for a one-component water-based coating composition has increased significantly.
こうした一液形の水性塗料組成物としては、種々提案されており、例えば、水酸基及びカルボキシル基含有アクリル系共重合体、水性アミノ樹脂、アミン化合物及び親水性有機溶剤からなる水性塗料組成物において、アミン化合物により、水酸基及びカルボキシル基含有アクリル系共重合体に含まれるカルボキシル基を中和することが提案されている(特許文献1)。また、水酸基含有(メタ)アクリル酸エステル類、カルボキシル基含有ビニル系モノマー、長鎖アルキル基含有(メタ)アクリル酸エステル類及びビニルモノマーの共重合体と、水溶性アミノ樹脂と水性媒体とを含むアクリル系水溶性塗料組成物において、アミン化合物を用い、水酸基及びカルボキシル基含有アクリル系共重合体のカルボキシル基を中和することが提案されている(特許文献2)。更に、ガラス転移点が-10℃~80℃の範囲にある水酸基及びカルボキシル基含有アクリル樹脂、ガラス転移点が-50~20℃の範囲にある水酸基及びカルボキシル基含有アクリル樹脂、水性アミノ樹脂、塩基性化合物及び水性媒体を含む金属被覆用水性塗料組成物において、塩基性化合物により、水酸基及びカルボキシル基含有アクリル樹脂のカルボキシル基を中和することが提案されている(特許文献3)。また、特許文献4では、水性樹脂、メラミン樹脂及び弱酸触媒としてリン酸エステル触媒を含む水性塗料組成物が提案され、塩基性化合物を用いて水性樹脂を中和することが提案されている(特許文献4)。 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). Furthermore, 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 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 3). In addition, 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).
しかしながら、前記特許文献1乃至4に記載の塗料組成物で形成された塗膜では、得られたプレコート鋼板の加工性(密着性、耐クラック性)や、耐傷付性が十分に満足できるものではなかった。 However, the coating films formed from the coating compositions described in Patent Documents 1 to 4 cannot sufficiently satisfy the workability (adhesion, crack resistance) and scratch resistance of the resulting precoated steel sheet. I didn't.
更に、一液形塗料組成物においては、主剤及び硬化剤が同一系内に共存しているため、塗膜物性を向上することを目的として主剤及び硬化剤の反応性を向上させると塗料組成物の貯蔵安定性が低下し、一方で、塗料組成物の貯蔵安定性を向上することを目的として反応性を低下させると塗膜物性が低下する、というトレードオフの関係が存在する。そのため、一液形塗料組成物において、貯蔵安定性と塗膜物性とを両立することは非常に困難であった。 Furthermore, in a one-component coating composition, the main agent and the curing agent coexist in the same system. On the other hand, if 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.
本発明者らは、こうした問題点を解決するために鋭意検討を重ね、架橋剤として、フルアルキル型メラミン樹脂を用い、更に、スルホン酸化合物とアミン化合物とを、特定の中和率となるように用いることで、一液型の組成物においても、高い貯蔵安定性達成することができ、更に、プレコート鋼板特有の高温且つ短時間の条件で塗装を行った場合でも、良好な塗膜物性(特に、加工性(密着性、耐クラック性)、耐傷付性)を発揮しうることを見出し、本発明を完成した。 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. By using it, even in a one-component composition, 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, the inventors have found that workability (adhesion, crack resistance) and scratch resistance can be exhibited, and completed the present invention.
本発明は、一液形であっても貯蔵安定性に優れ、折り曲げ等の加工性や加工の際の耐クラック性及び耐傷付性の良好な塗膜を形成し得る水性塗料組成物の提供を課題とする。 It is an object of the present invention to provide a water-based paint 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.
本発明は、以下の態様を提供する。
[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、
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。
The present invention provides the following aspects.
[1]
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.
[2] The aqueous coating composition according to [1], wherein the coating film-forming resin (A) has a weight average molecular weight of 100,000 or more.
[3] At a temperature of 23° C., 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, and the shear rate is 1,000 s − The aqueous coating composition according to [1] or [2], which has a shear viscosity of 150 mPa·s or more as measured in 1 .
[4] The aqueous coating composition according to any one of [1] to [3], further comprising an organic solvent (E1).
[5] The aqueous coating composition according to any one of [1] to [4], which is for coil coating.
[6] A step of applying the aqueous coating composition according to any one of [1] to [5] to an object to be coated to form a coating film;
Manufacture of a coating film, including a step of drying and/or curing the coating film under conditions in which the maximum temperature reached is 180° C. or higher and the drying and/or curing time is 120 seconds or less. Method.
本発明によると、一液形であっても貯蔵安定性に優れ、折り曲げ等の加工性や加工の際の耐クラック性及び耐傷付性の良好な塗膜を形成し得る水性塗料組成物が提供される。 According to the present invention, there is provided a water-based coating composition which is excellent in storage stability even in a one-pack type and capable of forming a coating film having excellent workability such as bending and crack resistance and scratch resistance during processing. be done.
本発明の水性塗料組成物は、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。 The aqueous coating composition of the present invention contains a coating film-forming resin (A), a cross-linking agent (B), a sulfonic acid compound (C) and an amine compound (D).
<塗膜形成樹脂(A)>
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。
<Coating film forming resin (A)>
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. In this specification, (meth)acrylic acid represents acrylic acid or methacrylic acid.
前記エチレン性不飽和結合を有する単量体としては、(メタ)アクリル酸、クロトン酸、イソクロトン酸、2-プロペン酸、エタクリル酸、プロピルアクリル酸、イソプロピルアクリル酸等の不飽和カルボン酸;マレイン酸、フマル酸、イタコン酸等の不飽和ポリカルボン酸(これらの無水物も含む);マレイン酸エチル、マレイン酸ブチル、フマル酸エチル、フマル酸ブチル、イタコン酸エチル、イタコン酸ブチル等の不飽和ポリカルボン酸のモノアルキルエステル;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸n-ペンチル、(メタ)アクリル酸ネオペンチル、(メタ)アクリル酸イソペンチル、(メタ)アクリル酸sec-ペンチル、(メタ)アクリル酸3-ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ステアリル等の(メタ)アクリル酸アルキルエステル;(メタ)アクリル酸シクロペンチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸トリシクロデシル、(メタ)アクリル酸アダマンチル等の脂環式炭化水素基を有する(メタ)アクリル酸エステル;(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル等の(メタ)アクリル酸ヒドロキシアルキル;これらのラクトン付加物(該ラクトンとしては、ε-カプロラクトン等)等の水酸基を有する(メタ)アクリル酸エステル;γ-(メタ)アクリロキシプロピルトリメトキシシラン、γ-(メタ)アクリロキシプロピルメチルジメトキシシラン、γ-(メタ)アクリロキシプロピルトリエトキシシラン、γ-(メタ)アクリロキシプロピルメチルジエトキシシラン、ビニルトリメトキシシラン、ビニルメチルジメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジトキシシラン等のオルガノシリル基を有する単量体;α-ビニルベンゼンスルホン酸、p-(メタ)アクリルアミドプロパンスルホン酸、t-ブチル(メタ)アクリルアミドスルホン酸等のスルホン酸基を有する単量体;前記水酸基を有する(メタ)アクリル酸エステルノリン酸モノエステル等のリン酸基を有する単量体;(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、メトキシブチル(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド等の(メタ)アクリルアミド単量体;アミノエチル(メタ)アクリルアミド、ジメチルアミノエチル(メタ)アクリルアミド、メチルアミノプロピル(メタ)アクリルアミド等のアミノ基を有する(メタ)アクリルアミド単量体;(メタ)アクリル酸グリシジル等のエポキシ基(オキシラニル基)を有する(メタ)アクリル酸エステル;(メタ)アクリロニトリル、α-クロロ(メタ)アクリロニトリル等の(メタ)アクリロニトリル単量体;酢酸ビニル、プロピオン酸ビニル等のカルボン酸ビニルエステル;スチレン、α-メチルスチレン、α-メチルスチレンダイマー、ビニルトルエン、ジビニルベンゼン等のスチレン系単量体;カルボニル基モノマー;前記以外の多官能ビニルモノマー等の架橋性モノマー;等が挙げられる。
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。
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)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, sec-pentyl (meth)acrylate, 3-pentyl (meth)acrylate, hexyl (meth)acrylate , (meth) heptyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (meth) (meth)acrylic acid alkyl esters such as dodecyl acrylate and stearyl (meth)acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecyl (meth)acrylate, (Meth) acrylic acid esters having an alicyclic hydrocarbon group such as adamantyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- (meth) acrylate Hydroxyalkyl (meth)acrylates such as hydroxybutyl; (meth)acrylic acid esters having a hydroxyl group such as lactone adducts thereof (such as ε-caprolactone as the lactone); γ-(meth)acryloxypropyltrimethoxy Silane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyl Organosilyl group-containing monomers such as triethoxysilane and vinylmethyldithoxysilane; α-vinylbenzenesulfonic acid, p-(meth)acrylamidopropanesulfonic acid, t-butyl Monomers having a sulfonic acid group such as (meth)acrylamidosulfonic acid; Monomers having a phosphoric acid group such as (meth)acrylic ester nophosphoric acid monoester having a hydroxyl group; (meth)acrylamide, N- (Meth)acrylamide monomers such as methylol (meth)acrylamide, methoxybutyl (meth)acrylamide, diacetone (meth)acrylamide; aminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, methylaminopropyl (meth)acrylamide (meth)acrylamide monomers having an amino group such as; (meth)acrylic acid esters having an epoxy group (oxiranyl group) such as glycidyl (meth)acrylate; (meth)acrylonitrile, α-chloro(meth)acrylonitrile, etc. (meth) acrylonitrile monomer; carboxylic acid vinyl ester such as vinyl acetate and vinyl propionate; styrene, α-methylstyrene, α-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.
前記アクリル樹脂(A1)は、水酸基を有する。前記アクリル樹脂(A1)が水酸基を有することで、該水酸基と架橋剤の反応基との間で架橋反応して塗膜を硬化させることができる。前記アクリル樹脂(A1)が水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、水酸基を有する(メタ)アクリル酸エステルを用いればよい。 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.
前記水酸基を有するアクリル樹脂(A1)の水酸基価は、好ましくは5mgKOH/g以上であり、より好ましくは7mgKOH/g以上、更に好ましくは10mgKOH/g以上であり、好ましくは50mgKOH/g以下、より好ましくは35mgKOH/g以下、更に好ましくは30mgKOH/g以下、一層好ましくは25mgKOH/g以下である。前記範囲内にあることで、加工性(密着性、耐クラック性)の良好な塗膜が得られるという利点がある。 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. By being within the above range, there is an advantage that a coating film having good workability (adhesion, crack resistance) can be obtained.
前記水酸基を有する(メタ)アクリル酸エステルは、(メタ)アクリロイル基に結合する基の炭素数が1~3であることが好ましく、2であることがより好ましい。水酸基を有し、前記(メタ)アクリロイル基に結合する基の炭素数が1~3である(メタ)アクリル酸エステルを含むことで、耐傷付性に優れる塗膜が得られるという利点がある。該水酸基を有し、(メタ)アクリロイル基に結合する基の炭素数が1~3である(メタ)アクリル酸エステルの含有率は、水酸基を有する(メタ)アクリル酸エステル中、好ましくは70質量%以上、より好ましくは80質量%以上であり、上限は100質量%である。 The (meth)acrylic acid ester having a hydroxyl group preferably has 1 to 3, more preferably 2 carbon atoms in the group bonded to the (meth)acryloyl group. By including 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 %.
前記アクリル樹脂(A1)の重量平均分子量は、例えば50,000以上、好ましくは100,000以上、更に好ましくは150,000以上であり、例えば10,000,000以下、好ましくは2,000,000以下である。アクリル樹脂(A1)の重量平均分子量が大きいほど、耐傷付性が良好であり、加工性に優れる塗膜が得られるという利点がある。 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.
なお本明細書において、重量平均分子量は、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。 In addition, in this specification, a weight average molecular weight is a value converted into polystyrene by gel permeation chromatography (GPC).
前記アクリル樹脂(A1)は、酸基を有するのが好ましい。前記アクリル樹脂(A1)が酸基を有することで、後述する水性媒体(E)への分散性を付与することができる。
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。
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.
In order for the acrylic resin (A1) to obtain an acid group, when forming a polymer, 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.
前記酸基を有する単量体としては、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が好ましく、不飽和モノカルボン酸、不飽和ポリカルボン酸がより好ましく、不飽和モノカルボン酸が更に好ましく、(メタ)アクリル酸が特に好ましい。 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.
前記アクリル樹脂(A1)の酸価は、好ましくは5mgKOH/g以上であり、好ましくは50mgKOH/g以下、より好ましくは30mgKOH/g以下である。前記範囲内にあることで、アクリル樹脂(A1)を水性媒体(E)中へ安定に分散させることができるという利点がある。 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).
なお本明細書において、アクリル樹脂(A1)の酸価及び水酸基価は、それぞれ固形分酸価及び固形分水酸基価を表し、JIS K 0070:1999に準じて測定することができる。 In this specification, 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.
前記アクリル樹脂(A1)のガラス転移温度(Tg)は、好ましくは-70℃以上、より好ましくは0℃以上、更に好ましくは10℃以上、一層好ましくは15℃以上であり、好ましくは95℃以下、より好ましくは90℃以下、更に好ましくは85℃以下、一層好ましくは80℃以下である。前記範囲内にあることで、塗膜加工性及び耐傷付性に優れる塗膜が得られるという利点がある。 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. By being within the above range, there is an advantage that a coating film having excellent coating film processability and scratch resistance can be obtained.
前記ガラス転移温度は、アクリル樹脂(A1)を構成する各モノマーの質量分率を、各モノマーから誘導される単独重合体(ホモポリマー)のTg(K:ケルビン)値で割ることによって得られるそれぞれの商の合計の逆数として計算することができる。
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。
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.
For example, when the resin is a polymer of a plurality of monomers (monomer A, monomer B, . . . monomer N), the following general formula:
1/Tg=wa/Tga+wb/Tgb+...+wn/Tgn
Let the Tg represented by be the Tg of the resin.
here,
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,
means
wa+wb+ . . . +wn=1.
前記アクリル樹脂中(A1)を形成する単量体中、エチレン性不飽和結合を有する単量体は、(メタ)アクリル酸アルキルエステルを含むことが好ましく、アルキル基の炭素数が1~6、より好ましくは1~4の(メタ)アクリル酸アルキルエステルを含むことがより好ましい。前記範囲内の単量体を用いることで、得られる塗膜の耐傷付性が優れるという利点がある。アルキル基の炭素数が1~6の(メタ)アクリル酸アルキルエステルの含有率は、前記(メタ)アクリル酸アルキルエステル中、好ましくは20質量%以上、より好ましくは30質量%以上、更に好ましくは40質量%以上であり、好ましくは95質量%以下、より好ましくは85質量%以下、更に好ましくは80質量%以下である。 Among the monomers forming (A1) in the acrylic resin, 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. By using a monomer within the above range, there is an advantage that the scratch resistance of the resulting coating film is excellent. 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.
前記アクリル樹脂(A1)に含まれる単量体中、耐候性の観点から、スチレン系単量体の含有率は、好ましくは10質量%以下、より好ましくは5質量%以下、更に好ましくは3質量%以下であり、下限は0質量%である。 Among the monomers contained in the acrylic resin (A1), from the viewpoint of weather resistance, 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.
前記アクリル樹脂(A1)が、酸基を有するものである場合、前記水性塗料組成物は、塩基性化合物を含んでいてもよい。前記水性塗料組成物が、塩基性化合物を含むことで、該酸基の一部又は全部が中和され、アクリル樹脂に対して水分散性を良好に付与することができる。前記塩基性化合物としては、例えば、アンモニア、アミン化合物、アルカリ金属等を用いることができる。また、後述するアミン化合物(D)の一部を前記塩基性化合物とすることもできる。
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。
When the acrylic resin (A1) has an acid group, the aqueous coating composition may contain 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. Examples of the basic compound that can be used include ammonia, amine compounds, alkali metals, and the like. Also, part of the amine compound (D) described later can be the basic compound.
Also, a known anionic and/or nonionic surfactant may be used to impart water dispersibility to the acrylic resin.
前記アクリル樹脂(A1)の含有率は、前記塗膜形成樹脂(A)中、好ましくは5質量%以上、より好ましくは10質量%以上、更に好ましくは15質量%以上であり、上限は100質量%である。 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. %.
前記アクリル樹脂(A1)は、水性樹脂であることが好ましく、水性媒体(E)に溶解し得る水溶性樹脂であってもよく、コロイダルディスパージョン型、エマルション型(乳化重合型、強制乳化型)等の水性媒体(E)に分散しうる水分散性樹脂であってもよい。前記アクリル樹脂(A1)は、好ましくは水分散性樹脂であり、より好ましくはエマルション型水分散性樹脂であり、特に好ましくは乳化重合によるエマルション型水分散性樹脂である。前記アクリル樹脂が(A1)が、酸基及び/又は水酸基を有すること、及び/又は乳化剤と共存することで、水性樹脂とすることができる。 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.
前記アクリル樹脂(A1)が、エマルション型水分散性樹脂である場合、エマルション粒子の平均粒子径は、好ましくは500nm以下、より好ましくは300nm以下、更に好ましくは200nm以下であり、例えば10nm以上、30nm以上、50nm以上であってもよい。前記範囲内にあることで、エマルション粒子及び前記エマルション粒子を含む塗料組成物の貯蔵安定性が良好であるという利点がある。なお本明細書において、平均粒子径は、動的光散乱法によって決定される平均粒子径であり、具体的には、電気泳動光散乱光度計ELSZシリーズ(大塚電子社製)等を使用して測定することができる。 When the acrylic resin (A1) is an emulsion-type water-dispersible resin, 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. In the present specification, the average particle size is an average particle size determined by a dynamic light scattering method. can be measured.
前記アクリル樹脂(A1)の最低造膜温度(MFT)は、好ましくは50℃以上、より好ましくは60℃以上、更に好ましくは70℃以上であり、例えば200℃以下、150℃以下、120℃以下であってもよい。前記範囲内にあることで、得られる塗膜の耐傷付性が向上し、塗膜同士のブロッキングが抑制されるという利点がある。なお本明細書において、最低造膜温度は、前記エマルション型水分散性樹脂を乾燥させたとき、亀裂の無い均一被膜が形成される最低温度を意味し、JIS K 6828-2:2003に準拠して測定することができる。 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. In the present specification, 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 is based on JIS K 6828-2:2003. can be measured by
前記アクリル樹脂(A1)が、エマルション型水分散性樹脂である場合、該エマルションは、コア部とシェル部とからなる多層構造粒子が分散されたエマルションであってもよい。 When the acrylic resin (A1) is an emulsion-type water-dispersible resin, the emulsion may be an emulsion in which multilayer-structured particles each having a core portion and a shell portion are dispersed.
前記多層構造粒子は、例えば、特開2002-12816号公報に記載の方法等によって調製することができる。 The multilayer structure particles can be prepared, for example, by the method described in JP-A-2002-12816.
前記アクリル樹脂(A1)は、前記エチレン性不飽和結合を有する単量体を重合することにより製造することができ、前記重合反応は、例えば、前記エチレン性不飽和結合を有する単量体を水性媒体(E)の一部又は全部中でかくはん下加熱することにより実施することができる。前記重合反応は、乳化重合反応であることが好ましい。前記重合反応の際、重合開始剤を共存させることが好ましく、必要に応じて、乳化剤を共存させることが好ましい。反応温度は例えば、30~100℃であることが好ましく、反応時間は、例えば1~10時間であることが好ましい。 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.
前記重合開始剤としては、ラジカル重合開始剤が好ましい。水溶性のフリーラジカル重合開始剤として、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩を用いることができる。また、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素等の酸化剤と、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、ロンガリット、アスコルビン酸等の還元剤とを組み合わせたレドックス系開始剤を用いることができる。これらのラジカル重合開始剤は、水性媒体(E)の一部又は全部に溶解し、水性溶液として用いてもよい。 As the polymerization initiator, a radical polymerization initiator is preferable. 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. can. These radical polymerization initiators may be dissolved in part or all of the aqueous medium (E) and used as an aqueous solution.
前記乳化剤としては、炭素数が6以上の炭化水素基等の疎水性部分と、カルボン酸塩、スルホン酸塩又は硫酸塩部分エステル等の親水性部分とを同一分子中に有するアニオン系又は非イオン系の乳化剤を用いることができる。前記アニオン系乳化剤としては、アルキルフェノール類又は高級アルコール類の硫酸半エステルのアルカリ金属塩又はアンモニウム塩;アルキル又はアリルスルホナートのアルカリ金属塩又はアンモニウム塩;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の硫酸半エステルのアルカリ金属塩又はアンモニウム塩;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有する各種アニオン系反応性乳化剤等が挙げられる。
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。
As the emulsifier, 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. Examples of 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. or 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.
Examples of 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.
また、重合(好ましくは乳化重合)の際、メルカプタン系化合物や低級アルコール等の分子量調節のための助剤(連鎖移動剤)の併用は、重合(好ましくは乳化重合)を進める観点から、また塗膜の円滑且つ均一な形成を促進し被塗物への接着性を向上させる観点から、好ましい場合も多く、適宜状況に応じて行われる。 Also, during polymerization (preferably emulsion polymerization), the combined use of an auxiliary agent (chain transfer 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.
乳化重合を実施する場合、通常の一段連続モノマー均一滴下法、多段モノマーフィード法であるコアシェル重合法や、重合中にフィードするモノマー組成を連続的に変化させるパワーフィード重合法等、いずれの乳化重合法も用いることができる。 When carrying out emulsion polymerization, 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.
前記アクリル樹脂(A1)は、予め該アクリル樹脂(A1)と、後述する水性媒体(E)の一部とを含む水性溶液又は水性分散体として、水性塗料組成物の調製に用いてもよい。該水性溶液又は水性分散体は、更に前記乳化剤を含んでいてもよい。 The acrylic resin (A1) may be used in the preparation of an aqueous coating composition as an aqueous solution or aqueous 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.
前記アクリル樹脂(A1)としては、市販品を用いてもよい。また、1種のみを用いてもよいし、2種以上を併用してもよい。 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.
前記塗膜形成樹脂(A)は、前記アクリル樹脂(A1)以外に、その他の樹脂(A2)を含んでいてもよい。 The coating film-forming resin (A) may contain other resin (A2) in addition to the acrylic resin (A1).
前記その他の樹脂(A2)としては、水酸基未含有のアクリル樹脂、ウレタン樹脂、酢酸ビニル樹脂、フッ素樹脂、塩化ビニル樹脂等が挙げられ、それぞれ水性樹脂であることが好ましく、水分散性樹脂であることがより好ましく、エマルション型水分散性樹脂であることが更に好ましい。該その他の樹脂(A2)は、予めその他の樹脂(A2)と水性媒体(E)の一部とを含む水性溶液又は水性分散体として、水性塗料組成物の調製に用いてもよい。該水性溶液又は水性分散体は、乳化剤を含んでいてもよい。 Examples of 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.
前記水酸基未含有のアクリル樹脂は、(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、前記エチレン性不飽和結合を有する単量体のうち、水酸基を有しないものの混合物を重合することによって調製することができる。 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
前記水酸基未含有のアクリル樹脂の重量平均分子量は、好ましくは50,000以上、より好ましくは100,000以上、更に好ましくは150,000以上であり、好ましくは10,000,000以下、より好ましくは2,000,000以下、更に好ましくは500,000以下である。前記範囲にあることで、得られる塗膜の加工性が良好になるとの利点がある。 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.
前記水酸基未含有のアクリル樹脂のガラス転移温度は、好ましくは80℃以下、より好ましくは60℃以下、更に好ましくは50℃以下であり、好ましくは20℃以上、より好ましくは30℃以上、更に好ましくは40℃以上である。前記範囲にあることで、耐傷付性が良好になるとの利点がある。 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.
前記アクリル樹脂の最低造膜温度(MFT)は、好ましくは50℃以上、より好ましくは60℃以上、更に好ましくは70℃以上であり、例えば200℃以下、150℃以下、120℃以下であってもよい。前記範囲内にあることで、得られる塗膜の耐傷付性が向上し、塗膜同士のブロッキングが抑制されるという利点がある。 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. 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.
前記水酸基未含有のアクリル樹脂は、酸基を有するのが好ましい。前記水酸基未含有のアクリル樹脂の酸価は、好ましくは5mgKOH/g以上であり、好ましくは50mgKOH/g以下、より好ましくは30mgKOH/g以下である。 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.
前記水酸基未含有のアクリル樹脂を含む場合、その含有率は、前記アクリル樹脂(A1)と前記水酸基未含有のアクリル樹脂の合計中、好ましくは20質量%以上、より好ましくは30質量%以上であり、好ましくは90質量%以下、より好ましくは85質量%以下である。 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.
前記塗膜形成樹脂(A)の水酸基価は、5mgKOH/g以上であり、好ましくは7mgKOH/g以上、より好ましくは10mgKOH/g以上であり、35mgKOH/g以下であり、好ましくは30mgKOH/g以下、より好ましくは25mgKOH/g以下である。前記範囲内にあることで、加工性及び耐傷付性の良好な塗膜が得られるという利点がある。 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. By being within the above range, there is an advantage that a coating film having good workability and scratch resistance can be obtained.
前記塗膜形成樹脂(A)の酸価は、好ましくは5mgKOH/g以上であり、好ましくは50mgKOH/g以下、より好ましくは30mgKOH/g以下である。前記範囲内にあることで、前記塗膜形成樹脂(A)を水性媒体(E)中へ安定に分散させることができるという利点がある。 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).
前記塗膜形成樹脂(A)の重量平均分子量は、例えば50,000以上、好ましくは100,000以上、より好ましくは150,000以上であり、例えば10,000,000以下、好ましくは2,000,000以下である。前記範囲内にあることで、加工性の良好な塗膜が得られるという利点がある。 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.
前記塗膜形成樹脂(A)のガラス転移温度(Tg)は、好ましくは-70℃以上、より好ましくは20℃以上、更に好ましくは25℃以上、一層好ましくは30℃以上であり、好ましくは95℃以下、より好ましくは70℃以下、更に好ましくは60℃以下、一層好ましくは50℃以下である。前記範囲内にあることで、塗膜加工性及び耐傷付性に優れる塗膜が得られるという利点がある。 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. By being within the above range, there is an advantage that a coating film having excellent coating film processability and scratch resistance can be obtained.
前記塗膜形成樹脂(A)としては、1種のみを用いてもよく、2種以上を併用してもよい。前記塗膜形成樹脂(A)が2種以上含まれる場合、前記塗膜形成樹脂(A)の各パラメータは、ガラス転移温度を除き、各樹脂のパラメータ及び含有率に基づき、加重平均値として算出してもよい。また、ガラス転移温度は、各塗膜形成樹脂の質量基準の含有率をガラス転移温度(K:ケルビン値)で除した値を合計し、その逆数として算出してもよい。 As the coating film-forming resin (A), only one type may be used, or two or more types may be used in combination. When two or more types of the coating film-forming resin (A) are included, 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).
前記塗膜形成樹脂(A)の含有量は、前記水性塗料組成物の固形分100質量部中、好ましくは50質量部以上、より好ましくは70質量部以上、更に好ましくは80質量部以上であり、好ましくは100質量部以下、より好ましくは95質量部以下、更に好ましくは90質量部以下である。なお本明細書において、塗膜形成樹脂(A)の含有量は、固形分のみの含有量を表すものとする。 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 even more preferably 90 parts by mass or less. In this specification, the content of the coating film-forming resin (A) represents the content of only the solid content.
本明細書において、水性塗料組成物の固形分は、水性塗料組成物の全部から、水性媒体(E)を除いた部分を表すものとする。 In the present specification, the solid content of the water-based coating composition represents the portion excluding the aqueous medium (E) from the entire water-based coating composition.
<架橋剤(B)>
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。
<Crosslinking agent (B)>
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).
メラミン樹脂は、メラミンとアルデヒドとから合成される熱硬化性の樹脂であり、トリアジン核1分子中に反応性官能基として、以下の式で表される反応性官能基を3つ有する化合物又はその重縮合体であることが好ましい。
-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。]
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. ]
メラミン樹脂としては、反応性官能基として-N(CH2OR1)2のみを含むフルアルキル型;反応性官能基として-N(CH2OR1)(CH2OH)を含むメチロール基型;反応性官能基として-N(CH2OR1)(H)を含むイミノ基型;反応性官能基として、-N(CH2OR1)(CH2OH)と-N(CH2OR1)(H)とを含む、又は、-N(CH2OH)(H)を含むメチロール/イミノ基型の4種類を例示することができる。R1は、炭素数1~4のアルキル基であることが好ましく、メチル基、n-ブチル基又はイソブチル基であることが好ましい。 As the melamine resin, a full alkyl type containing only -N(CH 2 OR 1 ) 2 as a reactive functional group; a methylol group type containing -N(CH 2 OR 1 ) (CH 2 OH) as a reactive functional group; Imino group type containing —N(CH 2 OR 1 )(H) as reactive functional group; —N(CH 2 OR 1 )(CH 2 OH) and —N(CH 2 OR 1 ) as reactive functional group (H) or containing —N(CH 2 OH)(H), methylol/imino group type four types can be exemplified. R 1 is preferably an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, n-butyl group or isobutyl group.
本発明においては、前記メラミン樹脂の中でも、X1及びX2のいずれもが、-CH2-OR1である化合物又はその重縮合体であるフルアルキル型メラミン樹脂(B1)を含むのが好ましく、このような樹脂としては、メチル化メラミン樹脂、ブチル化メラミン樹脂、イソブチル化メラミン樹脂等が挙げられる。フルアルキル型メラミン樹脂を含むことで、得られる塗料組成物の貯蔵安定性が良好であり、且つ高温及び触媒存在下でのアクリル樹脂(A1)との反応性が良好になるという利点がある。 In the present invention, among the melamine resins, it is preferable that 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. Examples of such resins include methylated melamine resins, butylated melamine resins, isobutylated melamine resins, and the like. By containing a full alkyl melamine resin, there are advantages that the obtained coating composition has good storage stability and good reactivity with the acrylic resin (A1) at high temperatures and in the presence of a catalyst.
前記フルアルキル型メラミン樹脂(B1)における重合度は、1以上であり、好ましくは1.2以上、更に好ましくは1.5以上であり、好ましくは10以下、より好ましくは5以下、更に好ましくは3以下である。 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.
前記フルアルキル型メラミン樹脂(B1)の数平均分子量は、好ましくは300以上であり、好ましくは2,000以下、より好ましくは1,300以下、更に好ましくは1,000以下、特に好ましくは800以下である。
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。
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.
In the present specification, the number average molecular weight is a value converted to polystyrene by gel permeation chromatography (GPC).
前記フルアルキル型メラミン樹脂(B1)としては、市販品を用いることもでき、例えば、サイメル303、サイメル325、サイメル350、サイメル370、マイコート715(いずれもメチル化メラミン樹脂、オルネクスジャパン社製)、サイメル202、サイメル235、サイメル254、サイメル1123、サイメル1128、サイメル1170、マイコート212(いずれもメチル-ブチル化混合メラミン樹脂、オルネクスジャパン社製)、スミマールM-40S(メチル化メラミン樹脂、住友化学社製)、アミディアJ-820-60、アミディアL-127-60(いずれもブチル化メラミン樹脂、DIC社製)等を挙げることができる。これらは、1種のみを用いてもよく、2種以上を併用してもよい。 As the 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). These may use only 1 type and may use 2 or more types together.
前記フルアルキル型メラミン樹脂(B1)の含有率は、前記架橋剤(B)中、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは95質量%以上であり、上限は100質量%である。 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.
前記架橋剤(B)は、前記フルアルキル型メラミン樹脂(B1)以外に、他の架橋剤(B2)を含んでいてもよい。前記他の架橋剤(B2)としては、前記フルアルキル型メラミン樹脂(B1)以外のメラミン樹脂、尿素樹脂、ベンゾグアナミン樹脂等のアミノ樹脂を挙げることができる。前記アミノ樹脂は、前記塗膜形成樹脂(A)との反応性が高く、得られる塗膜の外観及び耐湿性が良好である。 The cross-linking agent (B) may contain another cross-linking agent (B2) in addition to the full-alkyl melamine resin (B1). Examples of 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.
前記架橋剤(B)としては、1種のみを用いてもよく、2種以上を併用してもよい。 As said crosslinking agent (B), only 1 type may be used and 2 or more types may be used together.
前記塗膜形成樹脂(A)の含有量に対する前記架橋剤(B)の含有量比((B)/(A))は、質量基準で、好ましくは5/95、より好ましくは10/90以上であり、好ましくは30/70以下、より好ましくは20/80以下である。前記範囲内にあることで、得られる塗膜の加工性及び耐傷付性が良好になるという利点がある。 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.
<スルホン酸化合物(C)>
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。
<Sulfonic acid compound (C)>
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.
前記スルホン酸化合物(C)は、モノスルホン酸化合物であってもポリスルホン酸化合物であってもよい。前記スルホン酸化合物としては、例えば、メタンスルホン酸等の脂肪族スルホン酸;パラトルエンスルホン酸、ドデシルベンゼンスルホン酸、ジノニルナフタレンスルホン酸、ジノニルナフタレンジスルホン酸等の芳香族スルホン酸;等が挙げられる。前記スルホン酸化合物(C)としては、1種のみを用いてもよく、2種以上を併用してもよい。 The sulfonic acid compound (C) may be a monosulfonic acid compound or a polysulfonic acid compound. Examples of 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.
前記スルホン酸化合物(C)の含有量は、前記塗膜形成樹脂(A)100質量部に対して、好ましくは0.1質量部以上、より好ましくは0.5質量部以上であり、好ましくは5質量部以下、より好ましくは3質量部以下である。前記スルホン酸化合物(C)の含有量が前記範囲にあることで、プレコート鋼板における加工性(密着性、耐クラック性)や耐傷付性が良好な塗膜を形成することができる。 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.
<アミン化合物(D)>
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。
<Amine compound (D)>
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 There is an advantage that both stability during storage (for example, 15 to 50° C.) and high reactivity during heat drying and curing after coating can be achieved. A part of the amine compound (D) may be present by forming a salt with the sulfonic acid compound (C).
前記アミン化合物(D)は、1つ以上のアミノ基を有する化合物であり、第2級又は第3級アミン化合物であることが好ましい。 The amine compound (D) is a compound having one or more amino groups, and is preferably a secondary or tertiary amine compound.
また、前記アミン化合物の窒素原子の置換基は、飽和又は不飽和の脂肪族炭化水素基であることが好ましく、該飽和又は不飽和の脂肪族炭化水素基に含まれる水素原子は、それぞれ独立に、-COOH、-OH等に置換されていてもよく、該飽和又は不飽和の脂肪族炭化水素基に含まれる-CH2-は、-O-に置き換わっていてもよい。また、前記アミン化合物の窒素原子の置換基が、互いに結合して、該窒素原子を含む環を形成していてもよい。 Further, 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.
前記アミン化合物(D)としては、例えば、ジエチルアミン、ジ-n-プロピルアミン、ジイソプロピルアミン、ジイソブチルアミン、ジ-n-ブチルアミン、ジ-sec-ブチルアミン、ジアミルアミン、N-エチル-1,2-ジメチルプロピルアミン、N-メチルヘキシルアミン、ジ-n-オクチルアミン、ジアリルアミン等の第2級脂肪族アミン化合物;トリエチルアミン、トリブチルアミン、トリアリルアミン、N,N-ジメチルエタノールアミン、N-メチルジアリルアミン、N,N-ジメチルアリルアミン等の第3級脂肪族アミン化合物;ピペリジン、2-ピペコリン、3-ピペコリン、4-ピペコリン、2,4-ルペチジン、2,6-ルペチジン、3,5-ルペチジン、3-ピペリジンメタノール等の第2級環状アミン化合物;N-メチルピペリジン、N-メチルピペラジン、N-メチルモルホリン等の第3級環状アミン化合物;ピリジン、4-エチルピリジン等の芳香族化合物であるアミン化合物等が挙げられる。 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-methylpiperazine, tertiary cyclic amine compounds such as N-methylmorpholine; aromatic compounds such as pyridine and 4-ethylpyridine. .
前記アミン化合物(D)の沸点は、好ましくは50℃以上、より好ましくは70℃以上、更に好ましくは100℃以上であり、好ましくは250℃以下、より好ましくは220℃以下である。前記範囲内にあることで、前記水性塗料組成物の貯蔵安定性をより高めることができるという利点がある。 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. By being within the above range, there is an advantage that the storage stability of the aqueous coating composition can be further enhanced.
前記アミン化合物(D)の含有量は、前記アミン化合物(D)による、前記スルホン酸化合物(C)の中和率、すなわち、以下の式で求められるモル換算の中和率が、100%以上、1,300%以下となる範囲である。
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
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
前記中和率は、好ましくは200%以上、より好ましくは300%以上であり、例えば1,300%以下、1,100%以下、1,000%以下としてもよく、900%以下、800%以下であってもよい。特定の理論に限定して解釈すべきではないが、前記範囲内にあることで、貯蔵時(例えば、15~30℃)では、前記アミン化合物(D)が、前記スルホン酸化合物(C)のスルホン酸基をブロックし、触媒作用を抑制することで、貯蔵安定性を高めることができ、また、塗装後の加熱乾燥・硬化時(例えば、180℃以上)においては、そのブロックが外れ、スルホン酸化合物(C)が、触媒としての機能を発揮しうると考えられる。 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.
前記フルアルキル型メラミン樹脂(B1)は、イミノ基型メラミン樹脂、メチロール基型メラミン樹脂等の一般的に架橋剤として用いられるメラミン樹脂と比較すると、反応性が低いことが知られている。しかしながら、本発明者らの検討の結果、前記フルアルキル型メラミン樹脂(B1)の反応性が低いのは低温反応の場合(例えば、60~80℃)であること、そして、フルアルキル型メラミン樹脂(B1)と、前記スルホン酸化合物(C)及び前記アミン化合物(D)とを、これら前記中和率となるように用いた場合には、高温での反応性が高くなることが見出された。前記フルアルキル型メラミン樹脂(B1)、前記スルホン酸化合物(D)、前記アミン化合物(D)及び前記中和率を組み合わせることで、貯蔵安定性が良好であり、高温・短時間での塗装に特に適する水性塗料組成物が得られ、更に、架橋密度を高くすることができるため、塗膜加工性(密着性、耐クラック性)に優れる塗膜が得られるという利点がある。 The full alkyl-type melamine resin (B1) is known to have low reactivity compared to melamine resins generally used as cross-linking agents such as imino group-type melamine resins and methylol group-type melamine resins. However, as a result of investigation by the present inventors, 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. By combining the full alkyl type melamine resin (B1), the sulfonic acid compound (D), the amine compound (D), and the neutralization rate, 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.
前記スルホン酸化合物(C)及び前記アミン化合物(D)は、直接水性塗料組成物の調製に用いてもよく、予めこれらを混合した混合物として、水性塗料組成物の調製に用いてもよい。この際、前記混合物中において、前記スルホン酸化合物(C)と前記アミン化合物(D)の一部又は全部とが、塩(例えば、アミン化合物(D)に含まれるアミノ基で、スルホン酸化合物(C)に含まれるスルホン酸基がブロックされている塩)を形成していてもよく、スルホン酸化合物(C)とアミン化合物(D)の一部又は全部との塩を形成させた後、塗料組成物に配合してもよい。前記スルホン酸化合物(C)とアミン化合物(D)の一部又は全部との塩としては、メタンスルホン酸等の脂肪族スルホン酸;ジノニルナフタレンジスルホン酸、ジノニルナフタレンスルホン酸等の芳香族スルホン酸と、これらのアミンブロック体を挙げることができる。前記スルホン酸化合物(C)とアミン化合物(D)の一部又は全部との塩としては、市販品を用いることもできる。 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 obtained by mixing them in advance for the preparation of the water-based coating composition. At this time, in the mixture, 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).
一実施態様において、スルホン酸化合物(C)の含有量が、塗膜形成樹脂(A)100質量部に対して、1質量部以上5質量部以下であり、且つ、中和率が100%以上1,300%以下であることが好ましく;スルホン酸化合物(C)の含有量が、塗膜形成樹脂(A)100質量部に対して0.1質量部以上5質量部以下であり、且つ、中和率が200%以上1,000%以下であることがより好ましく;スルホン酸化合物(C)の含有量が、塗膜形成樹脂(A)100質量部に対して2質量部以上9質量部以下であり、且つ、中和率が300%以上900%以下であることが更に好ましい。塗料組成物が、前記のようなスルホン酸化合物(C)、アミン化合物(D)の量及び中和率を有することで、低温(貯蔵温度、例えば、15~30℃)における貯蔵安定性が高く、且つ、高温における反応性がより高くなり、得られる塗膜の加工性(密着性、耐クラック性)や耐傷付性がより良好となる。 In one embodiment, 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). or less, and 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.
前記水性塗料組成物の固形分中、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)の合計の含有率は、例えば、好ましくは50質量%以上、より好ましくは70質量%以上、更に好ましくは80質量%以上であり、上限は100質量%以下である。 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.
<水性媒体(E)>
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。
<Aqueous medium (E)>
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).
前記有機溶剤(E1)としては、親水性の有機溶剤が好ましく、例えば、25℃における水への溶解度が0.1g/100gH2O以上の有機溶剤が挙げられる。このような有機溶剤としては、例えば、エチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール等のグリコール系溶剤;エチレングリコールモノブチルエーテル(ブチルセロソルブ)、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコールエーテル系溶剤;メタノール、エタノール、イソプロピルアルコール、ベンジルアルコール等のアルコール系溶剤;ジオキサン、テトラヒドロフラン等の環状エーテル系溶剤;2,2,4-トリメチルペンタン-1,3-ジオールモノイソブチレート等のアルコールエステル系溶剤;アセトン等のケトン系溶剤;並びに、N-メチル-2-ピロリドン等を挙げることができる。このような有機溶剤を用いることで、得られる塗料組成物は基材との濡れ性が良好になるという利点がある。 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. Examples of such 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. By using such an organic solvent, there is an advantage that the obtained coating composition has good wettability with the substrate.
一実施態様において、前記有機溶剤(E1)の沸点は、好ましくは150℃以上、より好ましくは180℃以上であり、好ましくは300℃以下、より好ましくは250℃以下である。このような有機溶剤としては、例えば、プロピレングリコール(1,2-プロパンジオール)、1,4-ブタンジオール、1,5-ペンタンジオール、ジエチレングリコール、ジプロピレングリコール等のグリコール系溶剤が挙げられ、ジエチレングリコールが特に好ましい。これらは、1種のみを用いてもよく、2種以上を用いてよい。 In one embodiment, 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. Examples of such 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.
前記有機溶剤(E1)の水への溶解度は、25℃において、好ましくは0.1g/100gH2O以上、より好ましくは1g/100gH2O以上、更に好ましくは5g/100gH2O以上である。前記有機溶剤(E1)は、水と任意に混和するものであってもよい。 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.
前記水性媒体(E)中の有機溶剤(E1)の含有率は、3質量%以上であり、好ましくは4質量%以上、より好ましくは5質量%以上であり、好ましくは30質量%以下、より好ましくは20質量%以下、更に好ましくは10質量%以下である。前記範囲にあることで、環境への負荷を低減でき、また、前記塗料組成物の貯蔵安定性や基材への濡れ性、更には得られる塗膜の外観が良好であるという利点がある。 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. Within the above range, there are advantages that the load on the environment can be reduced, the storage stability of the coating composition, the wettability to the substrate, and the appearance of the resulting coating film are good.
前記水性媒体(E)の含有率は、好ましくは40質量%以上、より好ましくは50質量%以上、更に好ましくは55質量%以上であり、好ましくは90質量%以下、より好ましくは80質量%以下、更に好ましくは85質量%以下である。 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.
前記水性塗料組成物は、必要に応じて、前記水性媒体(E)以外の有機溶媒を含んでいてもよい。前記(E)以外の有機溶媒としては、例えば、ジエチレングリコールジブチルエーテル、2,2,4-トリメチル-1,3-ペンタンジオールモノイソブチレート(テキサノール)等が挙げられる。前記(E)以外の有機溶剤の沸点は、好ましくは150℃以上、より好ましくは180℃以上であり、好ましくは300℃以下、より好ましくは250℃以下である。 The water-based coating composition may contain an organic solvent other than the water-based medium (E), if necessary. Examples of 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.
<その他>
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。
<Others>
The water-based coating composition may further contain other additives, if necessary. Examples of 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.
前記粘性調整剤(F)としては、親水基(部分)又は疎水基(部分)の結合力(相互作用)を利用した会合型粘性調整剤;ポリマーの可溶化・増粘作用を利用した増粘型粘性調整剤を挙げることができる。前記会合型粘性調整剤としては、粘性調整剤同士又は基体樹脂との間に水素結合を形成し、その結合力(相互作用)を利用した親水会合型粘性調整剤及び分子内の疎水基(部分)同士の相互作用を利用した疎水会合型粘性調整剤を挙げることができ、前記会合型粘性調整剤としては、アルカリによるポリマーの可溶化・増粘作用を利用したアルカリ増粘型粘性調整剤を挙げることができる。 As the viscosity modifier (F), an associative viscosity modifier utilizing the binding force (interaction) of a hydrophilic group (part) or a hydrophobic group (part); Mold viscosity modifiers may be mentioned. The associative 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.
前記親水会合型粘性調整剤としては、ポリアマイド型粘性調整剤が挙げられる。前記ポリアマイド型粘性調整剤としては、市販品を用いてもよく、例えば(以下、いずれも商品名)、BYK-430、BYK-431(ビックケミー社製)、ディスパロンAQ-580、ディスパロンAQ-600、ディスパロンAQ-607(楠本化成社製)、チクゾールW-300、チクゾールW-400LP(共栄社化学社製)等を挙げることができる。 Examples of the hydrophilic associative viscosity modifier include polyamide viscosity modifiers. As the 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.
前記疎水会合型粘性調整剤としては、市販品を用いてもよく、例えば、アデカノールUH-420、アデカノールUH-462、アデカノールUH-472、アデカノールUH-526、UH-540、アデカノールUH-814N(ADEKA社製)、プライマルRH-1020、プライマルRM-2020(ダウケミカル社製)、SNシックナー612、SNシックナー621、ノパール700N(サンノプコ社製)等が挙げられる。 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.
前記アルカリ増粘型粘性調整剤として、例えば、ビスコース、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ポリアクリル酸ナトリウム、ポリビニルアルコール、カルボキシメチルセルロース等が挙げられる。また、市販品を用いてもよく、例えば、チローゼMH及びチローゼH(メルク社製)等のセルロース系粘性調整剤;プライマルASE-60、プライマルTT-615、プライマルRM-5(ダウケミカル社製)、ユーカーポリフォーブ(ユニオンカーバイト社製)等が挙げられる。
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。
Examples of the alkali-thickening viscosity modifier 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.
前記粘性調整剤(F)としては、会合型粘性調整剤が好ましい。会合型粘性調整剤を含むことで、ロールコーターでの塗装作業性(ロールコーター塗工性)が良好となる利点がある。具体的には、高剪断速度時に塗料組成物の粘性をニュートニアンにすることができる。また、より好ましくは、疎水会合型粘性調整剤と併用することで、得られる塗膜の耐水性等の物性を良好にできる利点がある。 As the viscosity modifier (F), an associative viscosity modifier is preferred. By including the associative viscosity modifier, there is an advantage that coating workability with a roll coater (roll coater coatability) is improved. Specifically, 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.
本発明の水性塗料組成物に含まれる粘性調整剤(F)の含有量は、塗膜形成樹脂(A)及び架橋剤(B)の固形分合計100質量部に対して、0.01~20質量部であることが好ましく、0.1~10質量部であることがより好ましい。粘性調整剤(F)の量がこのような範囲内にあることで、ロールコーターでの塗装作業性(ロールコーター塗工性)並びに得られる塗膜の外観及び耐水性が良好になるという利点がある。 The content of the viscosity modifier (F) contained in the aqueous coating composition of the present invention 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 cross-linking agent (B). It is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass. When the 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.
前記体質顔料としては、炭酸カルシウム、硫酸バリウム、クレー、タルク、マイカ、ガラス繊維等を挙げることができる。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。 Examples of the extender pigment 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.
一実施態様において、体質顔料の量は、塗膜形成樹脂(A)及び硬化剤(B)の固形分合計100質量部に対して、好ましくは1質量部以上40質量部以下、より好ましくは10質量部以上30質量部以下である。体質顔料の量がこのような範囲内であることにより、塗膜の耐傷付性が向上しやすくなる。 In one embodiment, 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.
前記着色顔料としては、例えば、二酸化チタン、カーボンブラック、グラファイト、酸化鉄、コールダスト等の着色無機顔料;フタロシアニンブルー、フタロシアニングリーン、キナクリドン、ペリレン、アンスラピリミジン、カルバゾールバイオレット、アントラピリジン、アゾオレンジ、フラバンスロンイエロー、イソインドリンイエロー、アゾイエロー、インダスロンブルー、ジブロムアンザスロンレッド、ペリレンレッド、アゾレッド、アントラキノンレッド等の着色有機顔料;アルミニウム粉、アルミナ粉、ブロンズ粉、銅粉、スズ粉、亜鉛粉、リン化鉄、微粒化チタン等を挙げることができる。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。 Examples of the coloring pigment 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.
前記遮熱顔料は、近赤外波長域(波長:780nm~2,500nm)の光を吸収しないか、又は近赤外波長域(波長:780nm~2,500nm)の光の吸収率が小さい顔料を指す。前記遮熱顔料としては特に限定されず、以下の無機系遮熱顔料及び有機系遮熱顔料を用いることができる。 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.
無機系遮熱顔料としては、例えば、酸化チタン、酸化マグネシウム、酸化バリウム、酸化カルシウム、酸化亜鉛、酸化ジルコニウム、酸化イットリウム、酸化インジウム、チタン酸ナトリウム、酸化ケイ素、酸化ニッケル、酸化マンガン、酸化クロム、酸化鉄、酸化銅、酸化セリウム、酸化アルミニウム等の金属酸化物系顔料;酸化鉄-酸化マンガン、酸化鉄-酸化クロム(例えば、大日精化社製のダイピロキサイドカラーブラック#9595、アサヒ化成工業社製のBlack6350)、酸化鉄-酸化コバルト-酸化クロム(例えば、大日精化社製のダイピロキサイドカラーブラウン#9290、ダイピロキサイドカラーブラック#9590)、酸化銅-酸化マグネシウム(例えば、大日精化社製のダイピロキサイドカラーブラック#9598)、酸化マンガン-酸化ビスマス(例えば、アサヒ化成工業社製のBlack6301)、酸化マンガン-酸化イットリウム(例えば、アサヒ化成工業社製のBlack6303)等の複合酸化物顔料;シリコン、アルミニウム、鉄、マグネシウム、マンガン、ニッケル、チタン、クロム、カルシウム等の金属系顔料;更に鉄-クロム、ビスマス-マンガン、鉄-マンガン、マンガン-イットリウム等の合金系顔料が挙げられる。これらは、1種のみを用いてもよく、2種以上を併用してもよい。 Examples of 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. dipyroxide color brown #9290, dipyroxide color black #9590), copper oxide-magnesium oxide (for example, Dainichisei Chemical Dipyroxide Color Black #9598), manganese oxide - bismuth oxide (eg, Black6301 manufactured by Asahi Chemical Industry Co., Ltd.), manganese oxide - yttrium oxide (eg, Black6303 manufactured by Asahi Chemical Industry 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.
有機系遮熱顔料としては、例えば、アゾ系顔料、アゾメチン系顔料、レーキ系顔料、チオインジゴ系顔料、アントラキノン系顔料(アントアンスロン顔料、ジアミノアンスラキノニル顔料、インダンスロン顔料、フラバンスロン顔料、アントラピリミジン顔料等)、ペリレン系顔料、ペリノン系顔料、ジケトピロロピロール系顔料、ジオキサジン系顔料、フタロシアニン系顔料、キニフタロン系顔料、キナクリドン系顔料、イソインドリン系顔料、イソインドリノン系顔料、等が挙げられる。これらは、1種のみを用いてもよく、2種以上を併用してもよい。 Examples of organic thermal barrier pigments 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.
前記光輝性顔料としては、例えば、アルミ箔、ブロンズ箔、スズ箔、金箔、銀箔、チタン金属箔、ステンレススチール箔、ニッケル・銅等の合金箔、箔状フタロシアニンブルー等の箔顔料を挙げることができる。これらは、1種のみを用いてもよく、2種以上を併用してもよい。 Examples of the luster pigment 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.
ワックスとしては、塗料用として当業者に知られているワックスが使用でき、例えば、マイクロクリスタリン、ポリエチレン、ポリプロピレン、パラフィン、カルナウバ及びそれらの変性物等が挙げられる。これらは、1種のみを用いてもよく、2種以上を併用してもよい。 Waxes known to those skilled in the art for paints can be used, and examples thereof include microcrystalline, polyethylene, polypropylene, paraffin, carnauba and modified products thereof. These may use only 1 type and may use 2 or more types together.
前記水性塗料組成物の剪断粘度は、温度23℃において、剪断速度0.01s-1で測定した場合、好ましくは30,000mPa・s以下、より好ましくは20,000mPa・s以下、更に好ましくは10,000mPa・s以下であり、好ましくは3,000mPa・s以上、より好ましくは4,000mPa・s以上、更に好ましくは5,000mPa・s以上である。せん断速度10s-1で測定した場合は、好ましくは800mPa・以下、より好ましくは700mPa・s以下、更に好ましくは600mPa・s以下であり、好ましくは300mPa・s以上、より好ましくは400mPa・s以上、更に好ましくは500mPa・s以上である。剪断速度1,000s-1で測定した場合は、好ましくは1,000mPa・s以下、より好ましくは150mPa・s以上であり、好ましくは500mPa・s以下である。前記範囲内にあることでロールコーター塗装時の塗料のピックアップ性に適した粘度となる。
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。
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. 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. 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. 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).
<水性塗料組成物の調製方法>
本発明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。
<Method for preparing aqueous coating composition>
The method for preparing the aqueous coating composition of the present invention is not particularly limited, and it can be prepared by mixing each component. For example, 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.
前記水性塗料組成物から形成される塗膜及び該塗膜の製造方法も本発明の技術的範囲に包含される。 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 invention.
<被塗物>
本発明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。
<Subject to be coated>
Examples of the object to be coated (substrate) to be coated with the aqueous coating composition of the present invention 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.
前記被塗物は、表面処理されていることが好ましい。具体的には、被塗物は、アルカリ脱脂処理、湯洗処理、水洗処理等の前処理が施された後に、化成処理が施されていることが好ましい。前記化成処理は公知の方法で行ってよく、例えば、クロメート処理、リン酸亜鉛処理等の非クロメート処理等が含まれる。前記表面処理としては、使用する鋼板に応じて適宜選択することができるが、重金属を含まない処理が好ましい。このように化成処理を施した被塗物上に、本発明の塗料組成物を塗装することにより、塗膜の金属板面に対する密着性が向上するとともに耐食性も向上する。また、化成処理を施した金属板面に下塗り塗膜(プライマー塗膜)を形成し、その上に塗装することもできる。該下塗り塗膜の膜厚は、好ましくは3μm以上、より好ましくは5μm以上であり、好ましくは15μm以下、より好ましくは10μm以下である。 The article to be coated is preferably surface-treated. Specifically, 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. By applying the coating composition of the present invention onto an object to be coated which has been subjected to chemical conversion treatment in this way, the adhesion of the coating film to the surface of the metal plate is improved, and the corrosion resistance is also improved. It is also possible to form an undercoat film (primer film) on the surface of the metal plate that has undergone chemical conversion treatment, and then apply coating thereon. The film thickness of the undercoat film is preferably 3 μm or more, more preferably 5 μm or more, and preferably 15 μm or less, more preferably 10 μm or less.
<塗膜の製造方法>
本発明の塗膜の製造方法は、
被塗物に本発明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。
<Method for producing coating film>
The method for producing a coating film of the present invention comprises:
A step of applying the aqueous coating composition of the present invention 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.
本発明の前記水性塗料組成物を被塗物に塗工する方法としては、特に限定されないが、ロールコーター法、エアレススプレー法、静電スプレー法、カーテンフローコーター法等、従来公知の方法を採用することができ、好ましくはロールコーター法、カーテンフローコーター法を挙げることができ、より好ましくはロールコーター法である。 The method of applying the water-based coating composition of the present invention to an object to be coated is not particularly limited, but conventionally known methods such as roll coater method, airless spray method, electrostatic spray method, and curtain flow coater method are employed. A roll coater method and a curtain flow coater method are preferred, and a roll coater method is more preferred.
前記最高到達温度は、好ましくは200秒以上であり、例えば280秒以下、270秒以下、250秒以下であってもよい。乾燥及び/又は硬化時間は、120秒以下であり、60秒以下、30秒以下、10秒以下、6秒以下とすることもでき、1秒以上であることが好ましい。 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.
前記塗装膜を乾燥及び/又は硬化させる方法は、特に限定されないが、熱風加熱、赤外線加熱、誘導加熱等の加熱手段を用いることができる。 A 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.
乾燥及び/又は硬化後の塗膜の膜厚(乾燥膜厚)は、好ましくは1μm以上、より好ましくは5μm以上であり、好ましくは30μm以下、より好ましくは25μm以下である。 The film thickness (dry film thickness) of the coating film after drying and/or curing is preferably 1 µm or more, more preferably 5 µm or more, and preferably 30 µm or less, more preferably 25 µm or less.
前記被塗物と、該被塗物上に形成された前記塗膜とを有する積層体も、本発明の技術的範囲に包含される。 A laminate comprising 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 invention.
前記被塗物は、更に、一方の面上に前記塗膜を有する場合、他方の面上に、エポキシ樹脂を含む塗料組成物等、公知の塗料組成物から形成される塗膜を有していてもよい。 When 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. may
本発明の水性塗料組成物は、通常、金属基材の塗装条件として採用される条件(例えば、乾燥/硬化温度60~80℃、乾燥/硬化時間30分~1時間)よりも、高温且つ短時間の条件で塗装を行う場合にも、硬化性が高く、良好な塗膜物性(密着性、耐クラック性等の加工性、耐傷付性)を有する塗膜を得ることができる。 The water-based coating composition of the present invention 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).
本発明の水性塗料組成物は、貯蔵安定性が高く、且つ、得られる塗膜が、折り曲げ等の加工の際にも被塗物から剥離しにくく密着性が良好であり、またクラックの発生も抑制され耐クラック性が良好であり、且つ、耐傷付性にも優れたものとなる。そのため、本発明の水性塗料組成物は、金属への塗装、特に、プレコートに好適に用いることができる。 The water-based coating composition of the present invention has high storage stability, and the resulting coating film does not easily peel off from the coated object even during processing such as bending, and has good adhesion. 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 invention can be suitably used for coating metals, particularly precoating.
以下の実施例により本発明を更に具体的に説明するが、本発明はこれらに限定されない。実施例中「部」及び「%」は、ことわりのない限り質量基準による。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these. "Parts" and "%" in the examples are based on mass unless otherwise specified.
<塗膜形成樹脂(A-1)の製造例>
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。
<Production example of coating film-forming resin (A-1)>
0.6 parts by mass of Pelex SS-H (surfactant, manufactured by Kao Corporation) was dissolved in 60 parts by mass of deionized water. To this, a monomer mixture consisting of 53.0 parts by mass of methyl methacrylate, 39.2 parts by mass of n-butyl acrylate, 5.8 parts by mass of 2-hydroxyethyl methacrylate and 2.0 parts by mass of methacrylic acid was added and stirred. to prepare 150.5 parts by mass of a monomer pre-emulsion. Separately, an aqueous initiator solution was prepared by dissolving 1.0 parts by mass of ammonium persulfate as an initiator in 20 parts by mass of ion-exchanged water.
温度計、コンデンサー及びかくはん機を備えた反応容器に、イオン交換水40質量部、ペレックスSS-H 0.4質量部を仕込み、窒素雰囲気下で80℃に加熱した。ここに80℃を保持したまま、前記開始剤水溶液を180分かけて滴下し、滴下開始10分後からモノマープレエマルションを反応容器の別の口から150分かけて滴下して、乳化重合を行った。前記開始剤水溶液の滴下が終了した後、更に80℃で60分加熱かくはんした後、室温まで冷却し、これにジメチルエタノールアミン2.10質量部を添加して塗膜形成樹脂(A-1)が水性媒体に分散しているアクリルエマルション(固形分濃度:45質量%)を調製した。 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).
モノマー種、量、開始剤量を表1のとおり変更した以外は、前記と同様にして、塗膜形成樹脂(A-2)~(A-11)を調製した。各塗膜形成樹脂における水酸基価等の特数値を表1に示す。 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.
実施例、比較例に用いた下記表中に示される各成分の詳細は以下のとおりである。
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%
Details of each component shown in the following table used in Examples and Comparative Examples are as follows.
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 agent (b-1) Cymel 327 (manufactured by Ornex Japan, imino group type methylated melamine resin); Solid content concentration: 90% by mass Number average molecular weight: 470
(b-2) Mycoat 508 (manufactured by Allnex Japan, imino group-type butylated melamine resin): solid content concentration: 80% by mass, number average molecular weight: 1,500
Sulfonic acid compound (C)
(C-1) AC400S (manufactured by Tayca, dodecylbenzenesulfonic acid); solid content concentration: 25% by mass
(C-2) AC700 (manufactured by Tayca, p-toluenesulfonic acid); solid content concentration: 25% by mass
(C-3) Nacure-1051 (manufactured by Kusumoto Kasei Co., Ltd., dinonylnaphthalene sulfonic acid); solid content concentration: 51% by mass
Other acid compounds (c-1) Cycat296 (manufactured by Allnex Japan, phosphoric acid compound); Solid content concentration: 50% by mass
Amine compound (D)
(D-1) DMEA (dimethylethanolamine, manufactured by Mitsubishi Gas Chemical Co., Ltd.); boiling point: 134°C
(D-2) AMP (2-amino-2-methyl-1-propanol, manufactured by Kokusan Chemical Co., Ltd.); boiling point: 165°C
(D-3) TEA (triethylamine, manufactured by Mitsubishi Gas Chemical Company); Boiling point: 90°C
Aqueous medium (E)
(E1-1) Diethylene glycol (manufactured by Nippon Shokubai Co., Ltd.); boiling point: 244 ° C., solubility in water: infinite (optionally miscible with water)
(E1-2) propylene glycol (manufactured by Sankyo Chemical Co., Ltd.); boiling point: 187°C, solubility in water: infinite (optionally miscible with water)
(E1-3) Dipropylene glycol (manufactured by Showa Kagaku Co., Ltd.); boiling point: 232° C., solubility in water: infinite (optionally miscible with water)
(E1-4) 1,4-butanediol (manufactured by Sankyo Chemical Co., Ltd.); boiling point: 228° C., solubility in water: infinite (optionally miscible with water)
(E1-5) 1,5-pentanediol (manufactured by Ube Industries, Ltd.); boiling point: 242° C., solubility in water: infinite (optionally miscible with water)
Viscosity modifier (F)
(F-1) SN Thickener 612 (polyether urethane hydrophobic association type viscosity modifier, manufactured by San Nopco); solid content concentration: 40% by mass
(F-2) SN Thickener 621 (polyether urethane-based hydrophobic association viscosity modifier, San Nopco); solid content concentration: 30% by mass
(F-3) ADEKA NOL UH-526 (polyether urethane-based hydrophobic association viscosity modifier, manufactured by ADEKA); Solid content concentration: 30% by mass
(F-4) Primal RM-2020NPR (polyether urethane-based hydrophobic association type viscosity modifier, Dow Chemical Co.); solid content concentration: 20% by mass
(F-5) Primal ASE-60 (polyacrylic acid ester emulsion-based alkali-swelling thickener, Dow Chemical Co.); solid content concentration: 28% by mass
<顔料分散ペーストの製造例>
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。
<Production example of pigment dispersion paste>
Disperbyk190 (manufactured by BYK Chemie) 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 And after premixing 65.2 parts by mass of titanium dioxide (Ti-Pure R-706, manufactured by DuPont) as a pigment, using an SG mill (dispersion medium: glass beads) at 1,600 rpm, the pigment coarse particles. Dispersed until the maximum particle size reached 5 μm to obtain a pigment-dispersed paste.
<水性塗料組成物1の製造例>
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。
<Production example of water-based coating composition 1>
55.1 parts by mass of the pigment dispersion paste obtained in the above Production Example, 80.0 parts by mass of the coating film-forming resin (A-1) obtained in the above Production Example, and 20.0 parts by mass of the coating film-forming resin (A-8) After mixing 17.6 parts by mass of Cymel 303 as a cross-linking agent (B-1), 5.4 parts by mass of diethylene glycol (E1-1) and 5.4 parts by mass of propylene glycol (E1-2) as an aqueous medium. were mixed and stirred. Next, 1.2 parts by mass of dodecylbenzenesulfonic acid as the sulfonic acid compound (C-1) and 1.9 parts by mass of dimethylethanolamine as the amine compound (D-1) were stirred with a disper, and a viscosity modifier ( As F-1), 0.2 parts by mass of thickener SN-612 was mixed with stirring to obtain a coating composition 1.
(塗料組成物2~45、比較例1~10)
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。
(Paint compositions 2 to 45, Comparative Examples 1 to 10)
A coating composition was prepared in the same manner as coating composition 1 except that the types and amounts of each component were changed as shown in Tables 2-7.
<塗装鋼板の製造例>
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。
<Production example of coated steel plate>
After alkaline degreasing of a hot-dip galvanized steel sheet with a thickness of 0.4 mm, a phosphating agent Surfcoat EC2310 (manufactured by Nippon Paint Surf Chemicals Co., Ltd.) is applied to the surface and back surface of the steel sheet to perform a non-chromium chemical conversion treatment. Dried.
Next, on the surface of the steel plate, 1 of the coating composition obtained in the production example is applied using a bar coater so that the dry coating film becomes 18 μm, and baked for 30 seconds under the condition that the material reaches a maximum temperature of 230 ° C. to form a surface coating film and obtain a coated steel sheet.
1)剪断粘度測定
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。
1) 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.
2)貯蔵安定性
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。
2) Storage stability
In accordance with the method specified in JIS K 5600 2-2 (flow cup method), Ford cup No. 4 (manufactured by Ueshima Seisakusho Co., Ltd.).
Ion-exchanged water was added to the coating compositions obtained in Examples and Comparative Examples to adjust the viscosity to 60±10 seconds (initial viscosity (seconds)). Specifically, the initial viscosity was measured immediately after dilution with the ion-exchanged water and stirring at 1,000 rpm for 3 minutes using a disper. The paint temperature was 25°C.
前記初期粘度(60±10秒(25℃))に調整した塗料組成物を1/5缶に8~9分目入れ、密閉した後、40℃の恒温室に静置した。その後、14日(2週間)後に取り出し、前記と同様に粘度を測定した(経時粘度(秒))。
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。
The coating composition adjusted to the initial viscosity (60±10 seconds (25° C.)) was placed in a ⅕ 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
A: The viscosity change rate is 0% or more and less than 30%.
Good: Viscosity change rate is 30% or more and less than 50%.
Δ: Viscosity change rate is 50% or more and less than 100%.
x: Viscosity change rate is 100% or more.
5)塗装作業性(ロールコーター塗工性)
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
5) Coating workability (roll coater coatability)
The coating compositions obtained in Examples and Comparative Examples were tested using a small test coater (manufactured by N.K. Tech Co., Ltd.) equipped with three rolls (backup roll, application roll, and pickup roll) under the following conditions: and the roll coater coatability was evaluated according to the following criteria. ○ or more was defined as a pass. The test conditions were room temperature of 23° C. and humidity of 60 RH%.
・ 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: 60kgf
・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 Δ: 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
なお、ロールコーターにおいて、塗料は、ピックアップロールによって巻き上げられ、アプリケーションロールに転移し、更にバックアップロールに転移して、被塗物に塗装される。ピックアップロールによって塗料が適切に巻き上げられ、アプリケーションロール、バックアップロール圧によりバックアップロールへと塗料の転移が適切に行われることで、塗料は被塗物に均一に塗装されるが、ピックアップロールによって、塗料が少量しか巻き上がらない場合、ロール間の転移の際にムラが発生し、被塗物に均一に塗装されない。 In the roll coater, 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, and 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.
4)加工性(密着性)
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。
4) workability (adhesion)
Each coated steel plate obtained in Examples and Comparative Examples was cut into 5 cm×3 cm pieces, and pre-bent using a seam folding machine (manufactured by Ueshima Seisakusho Co., Ltd.) so that the coating film faces the front side. Two steel plates having the same thickness (0.4 mm) were sandwiched between the test pieces, and they were bent by a pressing machine (manufactured by Kyoritsu Kogyo Co., Ltd.). Cellophane tape (registered trademark) (LP-24, manufactured by Nichiban Co., Ltd.) was brought into close contact with the processed portion of the coated steel plate and peeled off at once to evaluate the adhesion of the processed portion coating film. 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.
5)加工性(耐クラック性)
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。
5) Workability (crack resistance)
Each coated steel plate obtained in Examples and Comparative Examples was cut into 5 cm×3 cm pieces, and pre-bent using a seam folding machine (manufactured by Ueshima Seisakusho Co., Ltd.) so that the coating film faces the front side. Five steel plates having the same thickness (0.4 mm) were sandwiched between the test pieces, and the test piece was bent with a press machine (manufactured by Kyoritsu Kogyo Co., Ltd.). The state (cracks) of the coating film at the processed portion was observed with a magnifying glass of 15x, and the workability was evaluated according to the following criteria. A score of 4 or more was regarded as passing. The test conditions were a temperature of 23° C. and a humidity of 60 RH%.
5: No cracks are observed in the processed portion.
4: Cracks are observed in less than 20% (more than 0%) of the area of the processed portion.
3: Cracks are observed in 20% or more and less than 50% of the area of the processed portion.
2: Cracks are observed in 50% or more and less than 80% of the area of the processed portion.
1: Cracks are observed in 80% or more of the area of the processed portion.
6)耐傷付性
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
6) Scratch resistance Using a continuous loading scratch strength tester TYPE: 18/18L (manufactured by Shinto Kagaku Co., Ltd.), the coated surface of each coated steel plate obtained in Examples and Comparative Examples was scratched with an R of 0.4 mm. A diamond stylus (conical scratch stylus with R processing, diameter 0.4 mm) which was R-processed was applied, and a load was applied and rubbed once at 300 mm/min with a moving width of 10 cm. The weight of the load when the coating film surface was scratched and the substrate was exposed was evaluated according to the following criteria. ○ or more was defined as a pass. A load of 500 gf was applied at a time, and the test conditions were a temperature of 23° C. and a humidity of 60 RH%.
◎: 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
実施例1~45は、本発明の実施例であり、貯蔵安定性が高く、加工性に優れ、且つ耐傷付性が良好であった。 Examples 1 to 45 are examples of the present invention, exhibiting high storage stability, excellent processability, and good scratch resistance.
比較例1、2は、アクリル樹脂(A1)の水酸基価が5mgKOH/gに満たない例であり、耐傷付性に劣っていた。比較例3、4は、アクリル樹脂(A1)の水酸基価が35mgKOH/gを超える例であり、貯蔵安定性及び加工性に劣っていた。比較例5、6は、アミン化合物(D)によるスルホン酸化合物(C)の中和率が、100%に満たない例であり、貯蔵安定性に劣っていた。比較例7は、アミン化合物(D)によるスルホン酸化合物(D)の中和率が、1,300%を超える例であり、貯蔵安定性に劣っていた。比較例8、9は、架橋剤(B)として、フルアルキル型メラミン樹脂(B1)を含まない例であり、加工性に劣っていた。比較例10は、スルホン酸化合物(C)を含まず、リン酸化合物を用いた例であり、貯蔵安定性及び耐傷付性に劣っていた。 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 acrylic resin (A1) had a hydroxyl value exceeding 35 mgKOH/g, and were inferior in storage stability and workability. Comparative Examples 5 and 6 are 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 is 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 in which the phosphoric acid compound was used without containing the sulfonic acid compound (C), and was inferior in storage stability and scratch resistance.
Claims (6)
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。 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) having a hydroxyl group,
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.
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。 A step of applying the aqueous coating composition according to any one of claims 1 to 5 to an object to be coated to form a coating film,
Manufacture of a coating film, including a step of drying and/or curing the coating film under conditions in which the maximum temperature reached is 180° C. or higher and the drying and/or curing time is 120 seconds or less. Method.
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JPH03200884A (en) * | 1989-10-11 | 1991-09-02 | Kansai Paint Co Ltd | Thermosetting paint composition |
JPH07179813A (en) * | 1993-12-24 | 1995-07-18 | Nippon Paint Co Ltd | Water-based coating composition |
JP2000017225A (en) * | 1998-07-01 | 2000-01-18 | Mitsubishi Rayon Co Ltd | Water-based coating composition for metal coating |
JP2001240624A (en) * | 2000-02-29 | 2001-09-04 | Mitsubishi Rayon Co Ltd | Acrylic water soluble copolymer and acrylic water soluble coating composition |
JP2001323207A (en) * | 2000-05-18 | 2001-11-22 | Mitsubishi Rayon Co Ltd | Water base coating material composition |
JP2015174958A (en) * | 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 | Aqueous coating material composition and method for forming coating film |
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JP3200884B2 (en) | 1991-09-30 | 2001-08-20 | 日本板硝子株式会社 | Cutting method of thick glass plate |
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Publication number | Priority date | Publication date | Assignee | Title |
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JPH03200884A (en) * | 1989-10-11 | 1991-09-02 | Kansai Paint Co Ltd | Thermosetting paint composition |
JPH07179813A (en) * | 1993-12-24 | 1995-07-18 | Nippon Paint Co Ltd | Water-based coating composition |
JP2000017225A (en) * | 1998-07-01 | 2000-01-18 | Mitsubishi Rayon Co Ltd | Water-based coating composition for metal coating |
JP2001240624A (en) * | 2000-02-29 | 2001-09-04 | Mitsubishi Rayon Co Ltd | Acrylic water soluble copolymer and acrylic water soluble coating composition |
JP2001323207A (en) * | 2000-05-18 | 2001-11-22 | Mitsubishi Rayon Co Ltd | Water base coating material composition |
JP2015174958A (en) * | 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 | Aqueous coating material composition and method for forming coating film |
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