JP5297120B2 - Water-based paint composition - Google Patents
Water-based paint composition Download PDFInfo
- Publication number
- JP5297120B2 JP5297120B2 JP2008221201A JP2008221201A JP5297120B2 JP 5297120 B2 JP5297120 B2 JP 5297120B2 JP 2008221201 A JP2008221201 A JP 2008221201A JP 2008221201 A JP2008221201 A JP 2008221201A JP 5297120 B2 JP5297120 B2 JP 5297120B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxyl group
- aqueous
- modified starch
- starch
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003973 paint Substances 0.000 title abstract description 22
- 239000000203 mixture Substances 0.000 title abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 112
- 229920000881 Modified starch Polymers 0.000 claims abstract description 62
- 235000019426 modified starch Nutrition 0.000 claims abstract description 62
- 239000004368 Modified starch Substances 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000008199 coating composition Substances 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 34
- -1 carbodiimide compound Chemical class 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 12
- 239000004925 Acrylic resin Substances 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 42
- 238000005299 abrasion Methods 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 description 71
- 239000011248 coating agent Substances 0.000 description 65
- 229920002472 Starch Polymers 0.000 description 31
- 235000019698 starch Nutrition 0.000 description 30
- 239000008107 starch Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229920002261 Corn starch Polymers 0.000 description 20
- 239000008120 corn starch Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000000049 pigment Substances 0.000 description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000004480 active ingredient Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 229940014800 succinic anhydride Drugs 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920001225 polyester resin Polymers 0.000 description 7
- 239000004645 polyester resin Substances 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 150000002596 lactones Chemical class 0.000 description 6
- 229920005792 styrene-acrylic resin Polymers 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920000856 Amylose Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 240000003183 Manihot esculenta Species 0.000 description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 239000008149 soap solution Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 description 1
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 0.000 description 1
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- 229920001228 polyisocyanate Polymers 0.000 description 1
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- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
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- 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
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Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、水性塗料組成物に関する。 The present invention relates to an aqueous coating composition.
近年、環境問題の観点から、有機溶剤型塗料から水性塗料への転換が進められている。また、塗料は、一般に、耐水性、耐アルカリ性、耐磨耗性、耐候性等の塗膜性能に優れることが必要である。 In recent years, from the viewpoint of environmental problems, conversion from organic solvent-based paints to water-based paints has been promoted. In general, the coating material is required to have excellent coating performance such as water resistance, alkali resistance, abrasion resistance, and weather resistance.
一方、環境に対する負荷をより軽減する観点から、近年、塗料の原料として、生分解性の材料を用いることが行われている。また、脱石油化の観点から、バイオマス（特に植物）由来の原料は、ライフサイクルの中で二酸化炭素の排出と吸収がプラスマイナスゼロとなり、大気中の二酸化炭素を増加させない点から、注目されている。例えば、生分解性であり且つバイオマス由来材料である澱粉を塗料用樹脂成分として使用したものとして、澱粉と、澱粉分子に含まれる水酸基と硬化反応するイソシアネート基等の官能基を有する硬化剤とを含有する硬化型澱粉組成物が公知である（特許文献１参照）。 On the other hand, from the viewpoint of further reducing the burden on the environment, in recent years, biodegradable materials have been used as raw materials for paints. In addition, from the viewpoint of depetroleum, biomass (especially plants) -derived raw materials are attracting attention because carbon dioxide emissions and absorption are zero or plus in the life cycle and do not increase carbon dioxide in the atmosphere. Yes. For example, assuming that starch, which is biodegradable and biomass-derived material, is used as a resin component for paints, starch and a curing agent having a functional group such as an isocyanate group that undergoes a curing reaction with a hydroxyl group contained in the starch molecule. A curable starch composition is known (see Patent Document 1).
しかし、この硬化型澱粉組成物には、澱粉の水性化に際し、親水化のために導入されたカルボキシル基が塗膜中に残って、耐水性等の塗膜性能を低下させるという問題がある。
本発明の目的は、生分解性且つバイオマス由来の材料を使用した上で、耐水性、耐アルカリ性、耐摩耗性、耐候性等の塗膜性能に優れた水性塗料組成物を提供することにある。 An object of the present invention is to provide an aqueous coating composition having excellent coating performance such as water resistance, alkali resistance, abrasion resistance, and weather resistance after using a biodegradable and biomass-derived material. .
本発明者は、上記課題を達成すべく鋭意研究した。その結果、塗料用樹脂成分として、カルボキシル基含有水性樹脂とカルボキシル基含有変性澱粉とを併用し、これにカルボキシル基と硬化反応する硬化剤を組み合わせることにより、目的を達成し得ることを見出し、これに基づいて、本発明を完成するに至った。 The inventor has intensively studied to achieve the above-described problems. As a result, it was found that the objective can be achieved by using a carboxyl group-containing aqueous resin and a carboxyl group-containing modified starch in combination as a coating resin component, and combining a curing agent that undergoes a curing reaction with the carboxyl group. Based on the above, the present invention has been completed.
本発明は、以下の水性塗料組成物を提供するものである。 The present invention provides the following aqueous coating composition.
１．（Ａ）カルボキシル基含有水性樹脂、
（Ｂ）カルボキシル基含有変性澱粉、及び
（Ｃ）カルボキシル基と硬化反応する官能基を有する硬化剤
を含有する水性塗料組成物。
1. (A) a carboxyl group-containing aqueous resin,
An aqueous coating composition containing (B) a carboxyl group-containing modified starch, and (C) a curing agent having a functional group that undergoes a curing reaction with the carboxyl group.
２．水性樹脂（Ａ）の酸価が、３〜２００ｍｇＫＯＨ／ｇである上記項１に記載の水性塗料組成物。 2. Item 2. The aqueous coating composition according to Item 1, wherein the acid value of the aqueous resin (A) is from 3 to 200 mgKOH / g.
３．水性樹脂（Ａ）のガラス転移温度（Ｔｇ）が、−５０〜＋５０℃である上記項１に記載の水性塗料組成物。 3. Item 2. The aqueous coating composition according to Item 1, wherein the glass transition temperature (Tg) of the aqueous resin (A) is -50 to + 50 ° C.
４．水性樹脂（Ａ）が、カルボキシル基含有水性アクリル樹脂、カルボキシル基含有水性ポリエステル樹脂、及びカルボキシル基含有水性ウレタン樹脂からなる群より選ばれる少なくとも１種である請求項１に記載の水性塗料組成物。 4). The aqueous coating composition according to claim 1, wherein the aqueous resin (A) is at least one selected from the group consisting of a carboxyl group-containing aqueous acrylic resin, a carboxyl group-containing aqueous polyester resin, and a carboxyl group-containing aqueous urethane resin.
５．変性澱粉（Ｂ）の重量平均分子量が、１００万以下である上記項１に記載の水性塗料組成物。 5. Item 2. The aqueous coating composition according to Item 1, wherein the modified starch (B) has a weight average molecular weight of 1,000,000 or less.
６．変性澱粉（Ｂ）の酸価が、３〜２００ｍｇＫＯＨ／ｇである上記項１に記載の水性塗料組成物。 6). Item 2. The aqueous coating composition according to Item 1, wherein the modified starch (B) has an acid value of 3 to 200 mgKOH / g.
７．水性樹脂（Ａ）と変性澱粉（Ｂ）との合計固形分重量に対する変性澱粉（Ｂ）の割合が、８０重量％以下である上記項１に記載の水性塗料組成物。 7). Item 2. The aqueous coating composition according to Item 1, wherein the ratio of the modified starch (B) to the total solid weight of the aqueous resin (A) and the modified starch (B) is 80% by weight or less.
８．硬化剤（Ｃ）が、カルボジイミド化合物、オキサゾリン化合物、エポキシ化合物及び金属キレート化合物からなる群より選ばれる少なくとも１種である上記項１に記載の水性塗料組成物。 8). Item 2. The aqueous coating composition according to Item 1, wherein the curing agent (C) is at least one selected from the group consisting of a carbodiimide compound, an oxazoline compound, an epoxy compound, and a metal chelate compound.
９．硬化剤（Ｃ）の配合割合が、水性樹脂（Ａ）と変性澱粉（Ｂ）との合計カルボキシル基１当量に対して、カルボキシル基と硬化反応する官能基が０．０５〜１当量となる量である上記項１に記載の水性塗料組成物。 9. The amount by which the functional group that undergoes a curing reaction with the carboxyl group is 0.05 to 1 equivalent with respect to 1 equivalent of the total carboxyl group of the aqueous resin (A) and the modified starch (B), with the blending ratio of the curing agent (C). Item 2. The aqueous coating composition according to Item 1 above.
水性塗料組成物
本発明の水性塗料組成物は、カルボキシル基含有水性樹脂（Ａ）、カルボキシル基含有変性澱粉（Ｂ）、及びカルボキシル基と硬化反応する官能基を有する硬化剤（Ｃ）を、必須成分として含有する。
Water-based paint composition The water-based paint composition of the present invention essentially comprises a carboxyl group-containing aqueous resin (A), a carboxyl group-containing modified starch (B), and a curing agent (C) having a functional group that undergoes a curing reaction with a carboxyl group. Contains as a component.
カルボキシル基含有水性樹脂（Ａ）
カルボキシル基含有水性樹脂（Ａ）は、カルボキシル基含有変性澱粉（Ｂ）と共に、カルボキシル基と硬化反応する硬化剤（Ｃ）と反応して、塗膜を形成する成分である。カルボキシル基含有水性樹脂の形態としては、特に限定されるものではなく、例えば、水溶液樹脂、エマルション樹脂、ディスパージョン樹脂等の形態を挙げることができる。また、コア・シェル型のエマルション樹脂又はディスパージョン樹脂であってもよい。
Carboxyl group-containing aqueous resin (A)
The carboxyl group-containing aqueous resin (A) is a component that forms a coating film by reacting with the carboxyl group-containing modified starch (B) and a curing agent (C) that undergoes a curing reaction with the carboxyl group. The form of the carboxyl group-containing aqueous resin is not particularly limited, and examples thereof include forms of an aqueous solution resin, an emulsion resin, and a dispersion resin. Moreover, a core-shell type emulsion resin or dispersion resin may be used.
カルボキシル基含有水性樹脂（Ａ）は、その酸価が、３〜２００ｍｇＫＯＨ／ｇ程度の範囲内であることが好ましい。酸価が３ｍｇＫＯＨ／ｇ未満の場合は、組成物の硬化性が低下して、塗膜の耐水性や耐摩耗性が低下する傾向にあり、一方２００ｍｇＫＯＨ／ｇを越える場合は、塗膜の耐水性が低下するおそれがある。カルボキシル基含有水性樹脂（Ａ）の酸価は、５〜１５０ｍｇＫＯＨ／ｇ程度であることがより好ましく、１０〜１００ｍｇＫＯＨ／ｇ程度の範囲内であることが更に好ましい。 The carboxyl group-containing aqueous resin (A) preferably has an acid value in the range of about 3 to 200 mgKOH / g. When the acid value is less than 3 mgKOH / g, the curability of the composition tends to decrease, and the water resistance and abrasion resistance of the coating film tend to decrease. On the other hand, when it exceeds 200 mgKOH / g, the water resistance of the coating film tends to decrease. May decrease. The acid value of the carboxyl group-containing aqueous resin (A) is more preferably about 5 to 150 mgKOH / g, and still more preferably within the range of about 10 to 100 mgKOH / g.
また、カルボキシル基含有水性樹脂（Ａ）のガラス転移温度（Ｔｇ）は、−５０〜＋５０℃程度であるのが好ましい。ガラス転移温度（Ｔｇ）が−５０℃より低いと、塗膜の粘着感（タック感）が強くなる傾向にあり、一方＋５０℃より高いと、塗膜に割れ等の問題が生じる傾向にある。該ガラス転移温度（Ｔｇ）は、−３０〜＋３０℃程度であることがより好ましい。 The glass transition temperature (Tg) of the carboxyl group-containing aqueous resin (A) is preferably about −50 to + 50 ° C. If the glass transition temperature (Tg) is lower than −50 ° C., the tackiness (tackiness) of the coating tends to be strong, whereas if it is higher than + 50 ° C., problems such as cracks tend to occur in the coating. The glass transition temperature (Tg) is more preferably about −30 to + 30 ° C.
尚、本発明におけるガラス転移温度（Ｔｇ）は、下式から算出される値である。
１／Ｔｇ＝Ｗ１／Ｔ１＋Ｗ２／Ｔ２＋・・・Ｗｎ／Ｔｎ
式中、Ｗ１、Ｗ２・・・Ｗｎは各モノマーの重量％［（各モノマーの配合量／モノマー全重量）×１００］であり、Ｔ１、Ｔ２・・・Ｔｎは各モノマーのホモポリマーのガラス転移温度（絶対温度）である。
The glass transition temperature (Tg) in the present invention is a value calculated from the following equation.
1 / Tg = W 1 / T 1 + W 2 / T 2 +... W n / T n
Wherein, W 1, W 2 ··· W n is the weight percent of each monomer [(amount / total weight of the monomers in each monomer) × 100], T 1, T 2 ··· T n each monomer The glass transition temperature (absolute temperature) of the homopolymer of
カルボキシル基含有水性樹脂（Ａ）としては、有機溶剤中で溶液重合して得られたカルボキシル基含有樹脂中のカルボキシル基を塩基性化合物で中和することによって水溶化又は水分散化したもの；有機溶剤中で溶液重合して得られたカルボキシル基含有樹脂を後乳化したもの；水性媒体中で乳化重合又は懸濁重合してエマルション又はディスパージョンとして得られたカルボキシル基含有樹脂等をあげることができる。 As the carboxyl group-containing aqueous resin (A), a water-soluble or water-dispersed product obtained by neutralizing a carboxyl group in a carboxyl group-containing resin obtained by solution polymerization in an organic solvent with a basic compound; organic Post-emulsified carboxyl group-containing resin obtained by solution polymerization in a solvent; carboxyl group-containing resin obtained as emulsion or dispersion by emulsion polymerization or suspension polymerization in aqueous medium .
カルボキシル基含有水性樹脂（Ａ）としては、例えば、カルボキシル基含有水性アクリル樹脂、カルボキシル基含有水性ポリエステル樹脂、カルボキシル基含有水性ウレタン樹脂等を挙げることができる。 Examples of the carboxyl group-containing aqueous resin (A) include a carboxyl group-containing aqueous acrylic resin, a carboxyl group-containing aqueous polyester resin, and a carboxyl group-containing aqueous urethane resin.
上記カルボキシル基含有水性アクリル樹脂としては、特に限定されず、例えば、カルボキシル基を有する共重合性不飽和単量体及びその他の共重合性不飽和単量体からなる単量体混合物を共重合することによって得られるアクリル樹脂等を挙げることができる。 The carboxyl group-containing aqueous acrylic resin is not particularly limited, and, for example, copolymerizes a monomer mixture composed of a copolymerizable unsaturated monomer having a carboxyl group and other copolymerizable unsaturated monomers. An acrylic resin obtained by this can be mentioned.
上記カルボキシル基を有する共重合性不飽和単量体としては、特に限定されず、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、クロトン酸等を挙げることができ、これらの１種又は２種以上を用いる。上記その他の共重合性不飽和単量体としては、特に限定されず、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２，３−ジヒドロキシプロピル（メタ）アクリレート、グリセロール（メタ）アクリレート等の水酸基含有共重合性不飽和単量体；（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド等のアミド基含有共重合性不飽和単量体；スチレン、α−メチルスチレン、クロロスチレン、ビニルトルエン等のスチレン系共重合性不飽和単量体；メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、2−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート等の（メタ）アクリル酸エステル系共重合性不飽和単量体；（メタ）アクリロニトリル、酢酸ビニル、プロピオン酸ビニル、バーサテック酸ビニル等のビニル系共重合性不飽和単量体等を挙げることができ、これらの１種又は２種以上を用いる。 The copolymerizable unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and crotonic acid. One or two or more of these can be used. The other copolymerizable unsaturated monomer is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyl-containing copolymerizable unsaturated monomers such as hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate and glycerol (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N -Amide group-containing copolymerizable unsaturated monomers such as ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide; styrene, α-methylstyrene, chlorostyrene, vinyltoluene Styrene copolymerizable unsaturated monomers such as methyl; ) Acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) (Meth) acrylic ester copolymerizable unsaturated monomers such as acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate; (meth) acrylonitrile, vinyl acetate And vinyl-based copolymerizable unsaturated monomers such as vinyl propionate and vinyl versatate, and one or more of these are used.
上記カルボキシル基含有水性ポリエステル樹脂は、アルコールと酸のエステル結合形成反応によって得られるものである。上記カルボキシル基含有水性ポリエステル樹脂は、多価アルコール、多価カルボン酸、ラクトン、ヒドロキシカルボン酸等を原料として得られるものである。本明細書において、ポリエステル樹脂には、いわゆるアルキド樹脂も含まれる。 The carboxyl group-containing aqueous polyester resin is obtained by an ester bond formation reaction between an alcohol and an acid. The carboxyl group-containing aqueous polyester resin is obtained using polyhydric alcohol, polycarboxylic acid, lactone, hydroxycarboxylic acid and the like as raw materials. In the present specification, the polyester resin includes so-called alkyd resins.
上記多価アルコールは、１分子中に２つ以上の水酸基を有する化合物である。上記多価アルコールとしては、特に限定されず、例えば、プロピレングリコール、ネオペンチルグリコール、ブチレングリコール、ヘキシレングリコール、オクチレングリコール、１，６−ヘキサンジオール、１，８−オクタンジオール、１，９−ノナンジオール、１，１０−デカンジオール、１，１２−ドデカンジオール、１，２−シクロヘキサンジオール、１，３−シクロヘキサンジオール、１，４−シクロヘキサンジオール、水添ビスフェノールＡ、カプロラクトンジオール及びビスヒドロキシエチルタウリン等のジオール；トリメチロールプロパン及びヘキサントリオール等のトリオール；ペンタエリトリトール等のテトラオール等を挙げることができる。上記アルコール成分は、１種又は２種以上を用いる。 The polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule. The polyhydric alcohol is not particularly limited. For example, propylene glycol, neopentyl glycol, butylene glycol, hexylene glycol, octylene glycol, 1,6-hexanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, caprolactone diol, and bishydroxyethyl taurine Diols such as: Triols such as trimethylolpropane and hexanetriol; Tetraols such as pentaerythritol. The said alcohol component uses 1 type, or 2 or more types.
上記多価カルボン酸は、１分子中に２つ以上のカルボキシル基を有する化合物である。上記多価カルボン酸としては特に限定されず、例えば、フタル酸、イソフタル酸等の芳香族ジカルボン酸；アジピン酸、アゼライン酸及びテトラヒドロフタル酸等の脂肪族ジカルボン酸；トリメリット酸等のトリカルボン酸等を挙げることができ、これらの１種又は２種以上を用いる。また、必要に応じて、ステアリン酸、ラウリル酸及びミリスチン酸等の飽和脂肪酸；オレイン酸、リノール酸及びリノレイン酸等の不飽和脂肪酸；ひまし油、パーム油及び大豆油等の天然油脂及びそれらの変性物の長鎖脂肪酸等を併用することができる。 The polyvalent carboxylic acid is a compound having two or more carboxyl groups in one molecule. The polyvalent carboxylic acid is not particularly limited, and examples thereof include aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid and tetrahydrophthalic acid; tricarboxylic acids such as trimellitic acid, etc. One or two or more of these may be used. If necessary, saturated fatty acids such as stearic acid, lauric acid and myristic acid; unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid; natural fats and oils such as castor oil, palm oil and soybean oil, and modified products thereof Long chain fatty acids can be used in combination.
上記ラクトンは、環状エステル結合を有する化合物である。上記ラクトンとしては特に限定されず、例えば、ε−カプロラクトン、γ−カプロラクトン、δ−バレロラクトン、γ−ブチロラクトン等を挙げることができる。上記ラクトンは、１種又は２種以上を用いる。また、上記ラクトンは、上記多価アルコール及び多価カルボン酸と併用してもよい。 The lactone is a compound having a cyclic ester bond. The lactone is not particularly limited, and examples thereof include ε-caprolactone, γ-caprolactone, δ-valerolactone, and γ-butyrolactone. The said lactone uses 1 type (s) or 2 or more types. The lactone may be used in combination with the polyhydric alcohol and polyhydric carboxylic acid.
上記ヒドロキシカルボン酸は、１分子中に水酸基とカルボキシル基とを有する化合物である。上記ヒドロキシカルボン酸としては、特に限定されず、例えば、ジメチロールプロピオン酸等のヒドロキシカルボン酸等を挙げることができる。上記ヒドロキシカルボン酸は、１種又は２種以上を用いる。また、上記ヒドロキシカルボン酸は、上記多価アルコール、上記多価カルボン酸及び上記ラクトンと併用してもよい。 The hydroxycarboxylic acid is a compound having a hydroxyl group and a carboxyl group in one molecule. The hydroxycarboxylic acid is not particularly limited, and examples thereof include hydroxycarboxylic acids such as dimethylolpropionic acid. The said hydroxycarboxylic acid uses 1 type (s) or 2 or more types. The hydroxycarboxylic acid may be used in combination with the polyhydric alcohol, the polyvalent carboxylic acid, and the lactone.
上記カルボキシル基含有水性ポリエステル樹脂は、上記原料によって得られたポリエステル樹脂が水酸基を有する場合、上記水酸基の一部又は全部を無水フタル酸、無水コハク酸、ヘキサヒドロ無水フタル酸、無水トリメリット酸等の酸無水物によってカルボキシル基に変性したものであってもよい。 When the polyester resin obtained from the raw material has a hydroxyl group, the carboxyl group-containing water-based polyester resin is a part or all of the hydroxyl group such as phthalic anhydride, succinic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, etc. It may be modified to a carboxyl group with an acid anhydride.
上記カルボキシル基含有ポリウレタン樹脂は、ジイソシアネート化合物とジオール成分との反応により得られる樹脂であり、ジオール成分としてカルボキシル基を有するジオールを使用したものである。上記カルボキシル基を有するジオールとしては特に限定されず、例えば、ジメチロールプロピオン酸等を挙げることができる。 The carboxyl group-containing polyurethane resin is a resin obtained by a reaction between a diisocyanate compound and a diol component, and uses a diol having a carboxyl group as the diol component. The diol having a carboxyl group is not particularly limited, and examples thereof include dimethylolpropionic acid.
上記カルボキシル基含有樹脂を水に分散又は溶解するために使用する上記塩基性化合物としては、特に限定されず、例えば、アンモニア水；モノメチルアミン、ジメチルアミン、トリメチルアミン、トリエチルアミン、ジイソプロピルアミン、モノエタノールアミン、ジエタノールアミン及びジメチルエタノールアミン等の有機アミン；水酸化ナトリウム、水酸化カリウム及び水酸化リチウム等の無機塩基類等を挙げることができ、これらは１種又は２種以上を使用することができる。塩基性化合物の配合によって定まるカルボキシル基含有水性樹脂（Ａ）のｐＨは、６〜１０程度であるのが好ましい。ｐＨが６未満であると、中和が十分ではなく、樹脂の貯蔵安定性が低下する傾向がある。他方、ｐＨが１０を超えると硬化剤（Ｃ）との硬化性が低下する傾向がある。 The basic compound used for dispersing or dissolving the carboxyl group-containing resin in water is not particularly limited. For example, ammonia water; monomethylamine, dimethylamine, trimethylamine, triethylamine, diisopropylamine, monoethanolamine, Examples include organic amines such as diethanolamine and dimethylethanolamine; inorganic bases such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and these can be used alone or in combination of two or more. The pH of the carboxyl group-containing aqueous resin (A) determined by the blending of the basic compound is preferably about 6 to 10. If the pH is less than 6, neutralization is not sufficient, and the storage stability of the resin tends to decrease. On the other hand, when pH exceeds 10, there exists a tendency for sclerosis | hardenability with a hardening | curing agent (C) to fall.
カルボキシル基含有変性澱粉（Ｂ）
カルボキシル基含有変性澱粉（Ｂ）は、カルボキシル基含有水性樹脂（Ａ）と共に、カルボキシル基と硬化反応する硬化剤（Ｃ）と反応して、塗膜を形成する成分である。カルボキシル基含有変性澱粉（Ｂ）は、澱粉を変性することにより、カルボキシル基を導入したものである。
Carboxyl group-containing modified starch (B)
The carboxyl group-containing modified starch (B) is a component that forms a coating film by reacting with the carboxyl group-containing aqueous resin (A) and a curing agent (C) that undergoes a curing reaction with the carboxyl group. The carboxyl group-containing modified starch (B) is obtained by introducing a carboxyl group by modifying the starch.
原料の澱粉としては、特に限定されるものではなく、例えば、コーンスターチ、ワキシーコーンスターチ、ハイアミロースコーンスターチ、馬鈴薯澱粉、タピオカ澱粉、小麦澱粉、米澱粉、甘藷澱粉等を使用することができるが、更にこれらの澱粉を、エステル化した化工澱粉、エーテル化した化工澱粉等も使用することができる。これらの原料澱粉は、１種単独で、又は２種以上を適宜組み合わせて使用することができる。 The raw material starch is not particularly limited, and for example, corn starch, waxy corn starch, high amylose corn starch, potato starch, tapioca starch, wheat starch, rice starch, sweet potato starch and the like can be used. It is also possible to use a modified starch obtained by esterifying, an etherified modified starch or the like. These raw material starches can be used singly or in appropriate combination of two or more.
澱粉へのカルボキシル基の導入は、澱粉が有する水酸基に、エステル化反応、エーテル化反応、酸化反応等の公知の反応を施すことによって、行うことができる。エステル化反応は、例えば、澱粉に無水コハク酸等の二塩基酸無水物を反応させて、コハク酸エステル化澱粉等を得る反応である。エーテル化反応は、例えば、澱粉にモノクロロ酢酸等のカルボン酸ハロゲン化物を反応させて、カルボキシメチル化澱粉等を得る反応である。また、酸化反応は、次亜塩素酸ナトリウム等の酸化剤により澱粉を処理する方法である。酸化反応におけるカルボキシル基の生成量は、酸化剤添加量、反応ｐＨ、触媒種類などにより調節することが可能である。上記触媒としては、例えば、ニッケル、銅、コバルトなどの金属イオン；臭化物イオン；ＴＥＭＰＯ（２，２，６，６−テトラメチルピペリジン１−オキシル）等を挙げることができる。 Introduction of a carboxyl group into starch can be performed by subjecting a hydroxyl group of starch to a known reaction such as an esterification reaction, an etherification reaction, or an oxidation reaction. The esterification reaction is a reaction in which, for example, starch is reacted with a dibasic acid anhydride such as succinic anhydride to obtain succinic esterified starch. The etherification reaction is a reaction in which, for example, starch is reacted with a carboxylic acid halide such as monochloroacetic acid to obtain carboxymethylated starch or the like. The oxidation reaction is a method of treating starch with an oxidizing agent such as sodium hypochlorite. The amount of carboxyl groups generated in the oxidation reaction can be adjusted by the amount of oxidizing agent added, reaction pH, catalyst type, and the like. Examples of the catalyst include metal ions such as nickel, copper and cobalt; bromide ions; TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl).
カルボキシル基含有変性澱粉（Ｂ）は、その重量平均分子量が１００万以下程度であるのが好ましい。重量平均分子量が、１００万を超えると糊化の際、粘度が高くなりすぎて、澱粉固形分を大きくできず、その結果塗料の固形分も低くなり、塗膜外観が低下する傾向にある。上記重量平均分子量は、５０００〜１００万程度であるのがより好ましく、１〜８０万程度であるのが更に好ましい。尚、本明細書において、澱粉の重量平均分子量は、標準サンプルとしてプルランを用いたＧＰＣ（ゲルパーミエーションクロマトグラフィー）法により測定したものである。分子量の調節方法は、特に限定されず、原料澱粉またはカルボキシル基が導入された変性澱粉を、酸分解、酸化分解、酵素分解など既知の方法で低分子化することで行うことができる。 The carboxyl group-containing modified starch (B) preferably has a weight average molecular weight of about 1,000,000 or less. When the weight average molecular weight exceeds 1,000,000, the viscosity becomes too high at the time of gelatinization, the starch solid content cannot be increased, and as a result, the solid content of the paint also decreases and the coating film appearance tends to deteriorate. The weight average molecular weight is more preferably about 5,000 to 1,000,000, and further preferably about 1 to 800,000. In the present specification, the weight average molecular weight of starch is measured by GPC (gel permeation chromatography) method using pullulan as a standard sample. The method of adjusting the molecular weight is not particularly limited, and can be performed by reducing the molecular weight of the raw starch or modified starch introduced with a carboxyl group by a known method such as acid decomposition, oxidative decomposition, or enzymatic decomposition.
カルボキシル基含有変性澱粉（Ｂ）は、その酸価が、３〜２００ｍｇＫＯＨ／ｇ程度の範囲内であることが好ましい。酸価が３ｍｇＫＯＨ／ｇ未満の場合は、組成物の硬化性が低下して、塗膜の耐水性、耐洗浄性、耐磨耗性が低下する傾向にあり、一方２００ｍｇＫＯＨ／ｇを越える場合は、塗膜の耐水性が低下するおそれがある。カルボキシル基含有水性樹脂（Ａ）の酸価は、５〜１５０ｍｇＫＯＨ／ｇ程度であることがより好ましく、１０〜１００ｍｇＫＯＨ／ｇ程度の範囲内であることが更に好ましい。 The carboxyl group-containing modified starch (B) preferably has an acid value in the range of about 3 to 200 mgKOH / g. When the acid value is less than 3 mg KOH / g, the curability of the composition tends to decrease, and the water resistance, washing resistance, and abrasion resistance of the coating film tend to decrease. The water resistance of the coating film may be reduced. The acid value of the carboxyl group-containing aqueous resin (A) is more preferably about 5 to 150 mgKOH / g, and still more preferably within the range of about 10 to 100 mgKOH / g.
カルボキシル基含有変性澱粉（Ｂ）の使用割合は、カルボキシル基含有水性樹脂（Ａ）と当該変性澱粉（Ｂ）との合計固形分重量に対して、当該変性澱粉（Ｂ）の割合が、８０重量％以下程度であるのが好ましい。変性澱粉（Ｂ）の割合が、８０重量％を越える場合は、耐水性、耐摩耗性等の塗膜性能が低下する傾向にある。変性澱粉（Ｂ）の使用割合は、環境への負荷軽減の観点から、８０重量％までの範囲でできるだけ多くすることが好ましく、通常、水性樹脂（Ａ）と変性澱粉（Ｂ）との合計固形分重量に対して、当該変性澱粉（Ｂ）を、少なくとも５重量％以上程度とするのが良い。 The use ratio of the carboxyl group-containing modified starch (B) is such that the ratio of the modified starch (B) is 80% with respect to the total solid weight of the carboxyl group-containing aqueous resin (A) and the modified starch (B). % Or less is preferable. When the ratio of the modified starch (B) exceeds 80% by weight, the coating performance such as water resistance and abrasion resistance tends to be lowered. The proportion of the modified starch (B) used is preferably as large as possible within the range of up to 80% by weight from the viewpoint of reducing the environmental burden, and is generally the total solid content of the aqueous resin (A) and the modified starch (B). The modified starch (B) is preferably at least about 5% by weight or more with respect to the weight.
カルボキシル基と硬化反応する官能基を有する硬化剤（Ｃ）
硬化剤（Ｃ）が有するカルボキシル基と硬化反応する官能基としては、カルボジイミド基、オキサゾリン基、エポキシ基、金属イオン等を挙げることができる。従って、硬化剤（Ｃ）としては、これらの官能基を有する化合物である、カルボジイミド化合物、オキサゾリン化合物、エポキシ化合物、金属キレート化合物等から選ばれる１種を用いるか、又は２種以上を適宜組み合わせて用いるのが、好ましい。
Curing agent having a functional group that undergoes a curing reaction with a carboxyl group (C)
Examples of the functional group that undergoes a curing reaction with the carboxyl group of the curing agent (C) include a carbodiimide group, an oxazoline group, an epoxy group, and a metal ion. Therefore, as the curing agent (C), one kind selected from carbodiimide compounds, oxazoline compounds, epoxy compounds, metal chelate compounds and the like, which are compounds having these functional groups, is used, or two or more kinds are appropriately combined. It is preferable to use it.
硬化剤（Ｃ）の配合割合は、水性樹脂（Ａ）と変性澱粉（Ｂ）との合計カルボキシル基１当量に対して、カルボキシル基と硬化反応する官能基が０．０５〜１当量程度となる量であるのが好ましい。配合する硬化剤（Ｃ）が有する該官能基が０．０５当量未満となると水性樹脂（Ａ）及び変性澱粉（Ｂ）のカルボキシル基との反応点が乏しく、残存するカルボキシル基により、塗膜の耐水性、耐候性が低下する傾向にあり、一方、１当量を超えると、残存する硬化剤（Ｃ）の親水性基の影響により耐水性の低下の恐れもあるので好ましくない。硬化剤（Ｃ）の配合割合は、水性樹脂（Ａ）と変性澱粉（Ｂ）との合計カルボキシル基１当量に対して、硬化剤（Ｃ）の該官能基が０．５〜１当量程度となる量であるのがより好ましい。 The mixing ratio of the curing agent (C) is about 0.05 to 1 equivalent of functional groups that undergo a curing reaction with the carboxyl group with respect to 1 equivalent of the total carboxyl group of the aqueous resin (A) and the modified starch (B). An amount is preferred. When the functional group of the curing agent (C) to be blended is less than 0.05 equivalent, the reaction point with the carboxyl group of the aqueous resin (A) and the modified starch (B) is poor, and the remaining carboxyl group causes Water resistance and weather resistance tend to decrease. On the other hand, if it exceeds 1 equivalent, water resistance may be decreased due to the influence of the hydrophilic group of the remaining curing agent (C), which is not preferable. The mixing ratio of the curing agent (C) is such that the functional group of the curing agent (C) is about 0.5 to 1 equivalent with respect to 1 equivalent of the total carboxyl group of the aqueous resin (A) and the modified starch (B). More preferably, the amount is
カルボジイミド化合物としては、市販品を用いることができ、その商品名として、例えば、「カルボジライトＶ−０２」（有効成分４０％、水溶性タイプ、日清紡（株）製）、「カルボジライトＶ−０２−Ｌ２」（有効成分４０％、水溶性タイプ、日清紡（株）製）、「カルボジライトＥ−０１」（有効成分４０％、水分散性タイプ、日清紡（株）製）、「カルボジライトＥ−０２」（有効成分４０％、水分散性タイプ、日清紡（株）製）等を挙げることができる。 As the carbodiimide compound, a commercially available product can be used. For example, “Carbodilite V-02” (active ingredient 40%, water-soluble type, manufactured by Nisshinbo Co., Ltd.), “Carbodilite V-02-L2”. (40% active ingredient, water-soluble type, manufactured by Nisshinbo Co., Ltd.), “Carbodilite E-01” (active ingredient 40%, water dispersible type, manufactured by Nisshinbo Co., Ltd.), “Carbodilite E-02” (effective 40% component, water dispersible type, manufactured by Nisshinbo Co., Ltd.) and the like.
オキサゾリン化合物としては、市販品を用いることができ、その商品名として、例えば、「エポクロスＷＳ−７００」（有効成分２５％、水溶性タイプ、オキサゾリン基含有アクリル樹脂、日本触媒（株）製）、「エポクロスＫ−２０１０Ｅ」（有効成分４０％、水分散性タイプ、オキサゾリン基含有スチレン−アクリル樹脂、日本触媒（株）製）、「エポクロスＫ−２０２０Ｅ」（有効成分４０％、水分散性タイプ、オキサゾリン基含有スチレン−アクリル樹脂、日本触媒（株）製）等を挙げることができる。 As the oxazoline compound, a commercially available product can be used. For example, “Epocross WS-700” (25% active ingredient, water-soluble type, oxazoline group-containing acrylic resin, manufactured by Nippon Shokubai Co., Ltd.), “Epocross K-2010E” (active ingredient 40%, water dispersible type, oxazoline group-containing styrene-acrylic resin, manufactured by Nippon Shokubai Co., Ltd.), “Epocross K-2020E” (active ingredient 40%, water dispersible type, Oxazoline group-containing styrene-acrylic resin, manufactured by Nippon Shokubai Co., Ltd.).
エポキシ化合物としては、市販品を用いることができ、その商品名として、例えば、「デナコールＥＸ−５１２」（有効成分１００％、ポリグリセロールポリグリシジルエーテル、ナガセケムテックス（株）製）、「デナコールＥＸ−６１４Ｂ」（有効成分１００％、水溶性タイプ、ソルビトールポリグリシジルエーテル、ナガセケムテックス（株）製）等を挙げることができる。 As the epoxy compound, a commercially available product can be used. For example, “Denacol EX-512” (active ingredient 100%, polyglycerol polyglycidyl ether, manufactured by Nagase ChemteX Corporation), “Denacol EX” can be used. -614B "(100% active ingredient, water-soluble type, sorbitol polyglycidyl ether, manufactured by Nagase ChemteX Corporation).
金属キレート化合物としては、市販品を用いることができ、その商品名として、例えば、「ジルコゾールＡＣ−７」（有効成分２８％（溶媒は水）、水溶性タイプ、炭酸ジルコニールアンモニウム[(NH４)２ZrO(CO３)２]、第一稀元素工業（株）製）、「アルミキレートＭ」（有効成分１００％、アルミニウムアルキルアセトアセテート・ジイソプロピレート，川研ファインケミカル（株）製）等を挙げることができる。 As the metal chelate compound, a commercially available product can be used. For example, “Zircozol AC-7” (active ingredient 28% (solvent is water), water-soluble type, zirconyl ammonium carbonate [(NH 4 ) 2 ZrO (CO 3 ) 2 ], manufactured by Daiichi Rare Element Industrial Co., Ltd.), “Aluminum Chelate M” (100% active ingredient, aluminum alkyl acetoacetate / diisopropylate, manufactured by Kawaken Fine Chemical Co., Ltd.), etc. Can be mentioned.
任意成分
本発明の水性塗料組成物には、水性樹脂（Ａ）、変性澱粉（Ｂ）及び硬化剤（Ｃ）の必須成分に加えて、必要に応じて、着色顔料、体質顔料、顔料分散剤、消泡剤、増粘剤、紫外線吸収剤、光安定剤、凍結防止剤、造膜助剤、防かび剤、抗菌剤、防腐剤、表面調整剤等の任意成分を配合することができる。
Optional components In addition to the essential components of the water-based resin (A), modified starch (B), and curing agent (C), the water-based coating composition of the present invention includes, as necessary, a color pigment, an extender pigment, and a pigment dispersant. An optional component such as an antifoaming agent, a thickener, an ultraviolet absorber, a light stabilizer, an antifreezing agent, a film-forming aid, an antifungal agent, an antibacterial agent, an antiseptic, and a surface conditioner can be blended.
上記着色顔料としては、特に限定されず、例えば、黄色酸化鉄、酸化鉄、カーボンブラック、二酸化チタン等の無機顔料；アゾキレート系顔料、不溶性アゾ系顔料、縮合アゾ系顔料、フタロシアニン系顔料、インジゴ顔料、ペリノン系顔料、ペリレン系顔料、ジオキサン系顔料、キナクリドン系顔料、イソインドリノン系顔料、金属錯体顔料等の有機顔料等を挙げることができる。また、上記体質顔料としては、特に限定されず、例えば、炭酸カルシウム、沈降性硫酸バリウム、クレー、タルク、珪藻土等を挙げることができる。 The color pigment is not particularly limited, and examples thereof include inorganic pigments such as yellow iron oxide, iron oxide, carbon black, and titanium dioxide; azo chelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, and indigo pigments. And organic pigments such as perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments and metal complex pigments. The extender is not particularly limited, and examples thereof include calcium carbonate, precipitated barium sulfate, clay, talc, and diatomaceous earth.
本発明の水性塗料組成物の顔料体積濃度は、１０〜９０％程度であることが好ましい。１０％未満であると塗膜の隠蔽性が低下する恐れがあり、９０％を越えると造膜性及び膜強度が低下する恐れがある。 The pigment volume concentration of the aqueous coating composition of the present invention is preferably about 10 to 90%. If it is less than 10%, the concealability of the coating film may be lowered, and if it exceeds 90%, the film forming property and film strength may be lowered.
水性塗料組成物の調製及び適用
本発明の水性塗料組成物は、特に限定されないが、例えば、カルボキシル基含有水性樹脂（Ａ）、糊化したカルボキシル基含有変性澱粉（Ｂ）及び各種任意成分を、水媒体中で混合攪拌した後、硬化剤（Ｃ）を加えることにより、容易に調製することができる。水媒体としては、各成分製造時に含まれるものであってもよいし、必要なら適宜イオン交換水等を加えてもよい。混合機としては、例えば、ディスパー、ＳＧ分散機、ロール型混練機、ボールミル、加圧ニーダー等の塗料分野において公知のものを使用することができる。
Preparation and application of aqueous coating composition The aqueous coating composition of the present invention is not particularly limited. For example, a carboxyl group-containing aqueous resin (A), a gelatinized carboxyl group-containing modified starch (B), and various optional components, After mixing and stirring in an aqueous medium, it can be easily prepared by adding the curing agent (C). As an aqueous medium, what is contained at the time of each component manufacture may be sufficient, and ion-exchange water etc. may be added suitably if necessary. As the mixer, for example, those known in the paint field such as a disper, an SG disperser, a roll-type kneader, a ball mill, and a pressure kneader can be used.
カルボキシル基含有変性澱粉（Ｂ）は、予め糊化して用いられる。糊化の方法は特に限定されず、連続糊化装置により澱粉スラリーに蒸気を連続的に加えて糊化させる方法、澱粉スラリーを攪拌しながら加温し糊化させる方法等がある。温度、時間等の糊化条件は使用する澱粉の物性に合わせて適宜調節することができる。 The carboxyl group-containing modified starch (B) is used after being gelatinized in advance. The method of gelatinization is not particularly limited, and there are a method in which steam is continuously added to the starch slurry by a continuous gelatinizer to gelatinize, a method in which the starch slurry is heated and gelatinized while stirring, and the like. The gelatinization conditions such as temperature and time can be appropriately adjusted according to the physical properties of the starch used.
本発明の水性塗料組成物は、前記の様に一液型組成物とする以外に、例えば、カルボキシル基含有水性樹脂（Ａ）、糊化したカルボキシル基含有変性澱粉（Ｂ）及び各種任意成分を含有する成分と、硬化剤（Ｃ）を含有する硬化剤成分とを別々に保存しておき、使用時にこれらを混合する、いわゆる二液型組成物としてもよい。長期の貯蔵安定性を確保したい場合には、二液型組成物とすることが好ましい。 The aqueous coating composition of the present invention includes, for example, a carboxyl group-containing aqueous resin (A), a gelatinized carboxyl group-containing modified starch (B), and various optional components in addition to the one-component composition as described above. It is good also as what is called a two-component composition which preserve | saves separately the component to contain and the hardening | curing agent component containing a hardening | curing agent (C), and mixes these at the time of use. When it is desired to ensure long-term storage stability, a two-part composition is preferable.
本発明水性塗料組成物を適用する被塗物としては、特に限定されず、例えば、鉄、ステンレス、アルミニウム等およびその表面処理物等の金属基材；セメント類、石灰類、石膏類等のセメント系基材；ポリ塩化ビニル類、ポリエステル類、ポリカーボネート類、アクリル類等のプラスチック系基材等を挙げることができる。また、これらの各種基材からなる、建材、建築物、構造物等の建築・建材分野の各種被塗物；自動車車体、自動車部品、自動車内装品、自動車外装品等の自動車工業分野の各種被塗物；電化製品、電気部品、電子部品等の電気・電子工業分野の各種被塗物；家庭用品等のその他の分野の各種被塗物等を挙げることができる。 The coating object to which the aqueous coating composition of the present invention is applied is not particularly limited, and examples thereof include metal substrates such as iron, stainless steel, aluminum, and surface treated products thereof; cements such as cements, limes, and gypsums. Base materials; plastic base materials such as polyvinyl chlorides, polyesters, polycarbonates, and acrylics. In addition, various coatings in the field of building and building materials such as building materials, buildings, structures, etc. composed of these various base materials; various coatings in the automotive industry field such as automobile bodies, automobile parts, automobile interior parts, automobile exterior parts, etc. Coatings; Various coatings in the electric / electronic industry field such as electrical appliances, electrical parts, and electronic parts; various coatings in other fields such as household goods.
また、本発明塗料組成物の塗装方法としては、特に限定されず、例えば、刷毛塗り、ローラー塗装、スプレー塗装等を挙げることができる。塗装後、通常、常温乾燥又は加熱乾燥させることにより硬化塗膜を得ることができる。なお、塗布量；下塗り、中塗り、上塗り等の塗装順；塗装膜厚；乾燥時間等は、塗料の種類や適用する被塗物に応じて任意に設定することができる。 Moreover, it does not specifically limit as a coating method of this invention coating composition, For example, brush coating, roller coating, spray coating etc. can be mentioned. After coating, usually a cured coating film can be obtained by drying at room temperature or drying by heating. The coating amount; the order of coating such as undercoating, intermediate coating, and topcoating; the coating film thickness; the drying time, and the like can be arbitrarily set according to the type of paint and the object to be applied.
本発明の水性塗料組成物によれば、塗料用樹脂成分として、カルボキシル基含有水性樹脂（Ａ）とカルボキシル基含有変性澱粉（Ｂ）とを併用し、これにカルボキシル基と硬化反応する硬化剤（Ｃ）を組み合わせたことにより、次のような格別顕著な効果が奏される。 According to the aqueous coating composition of the present invention, a carboxyl group-containing aqueous resin (A) and a carboxyl group-containing modified starch (B) are used in combination as a coating resin component, and a curing agent that cures with carboxyl groups ( By combining C), the following remarkable effects are produced.
（１）耐水性、耐アルカリ性、耐磨耗性、耐候性等の塗膜性能に優れた塗膜が得られる。特に、カルボキシル基を硬化反応に用いるため、塗膜中にカルボキシル基が残存し難いことにより、良好な耐水性が発揮される。 (1) A coating film excellent in coating film performance such as water resistance, alkali resistance, abrasion resistance, and weather resistance can be obtained. In particular, since a carboxyl group is used for the curing reaction, good water resistance is exhibited because the carboxyl group hardly remains in the coating film.
（２）水性塗料組成物であり、しかも生分解性且つバイオマス由来であるカルボキシル基含有変性澱粉（Ｂ）を使用していることにより、脱石油化、二酸化炭素削減等の観点から、環境への負荷が大幅に軽減されている。 (2) By using the carboxyl group-containing modified starch (B) which is a water-based coating composition and is biodegradable and derived from biomass, it is environmentally friendly from the viewpoint of depetroleumation and carbon dioxide reduction. The load has been greatly reduced.
（３）従って、建築・建材分野、自動車工業分野、電気・電子工業分野、その他の分野において用いられる水性塗料組成物として、好適に使用できる。 (3) Therefore, it can be suitably used as an aqueous coating composition used in the construction / building materials field, the automobile industry field, the electric / electronic industry field, and other fields.
以下、製造例、実施例及び比較例を挙げて、本発明をさらに詳細に説明する。但し、本発明はこれらによって限定されるものではない。尚、各例において、部及び％は、原則として、重量基準である。 Hereinafter, the present invention will be described in more detail with reference to production examples, examples and comparative examples. However, the present invention is not limited by these. In each example, parts and% are based on weight in principle.
カルボキシル基含有水性アクリル樹脂（Ａ）の調製
製造例１
滴下漏斗、温度計、窒素導入管、還流冷却器および攪拌機を備えたセパラプルフラスコに、イオン交換水３４．５部、乳化剤（商品名「ペレックスＳＳ−Ｈ」、花王社製、アルキルジフェニルエーテルスルホン酸ナトリウム）０．３部を仕込み、窒素雰囲気下で８０℃に昇温した。スチレン１５部、２−エチルヘキシルアクリレート４１．１部、メチルメタクリレート４２．０部及びアクリル酸１．９部からなるモノマー混合液に、ドデシルメルカプタン０．６部を加えた後、これを、「ペレックスＳＳ−Ｈ」１．２部をイオン交換水５０部に溶解させた乳化剤水溶液中に加え、ミキサーを用いて乳化させて得たプレエマルションと、過硫酸アンモニウム０．３部をイオン交換水１３部に溶解させた開始剤水溶液とを、上記フラスコ中へ、別個の滴下漏斗から同時に滴下した。前者は１２０分間、後者は１５０分間に渡って均等に滴下した。滴下終了後、同温度でさらに１２０分間反応を継続した。冷却後、用いたアクリル酸の１０モル％に相当するアンモニア水で中和した。中和物を２００メッシュ金網で濾過して、酸価１５ｍｇＫＯＨ／ｇ、ガラス転移温度５℃、固形分５０％のカルボキシル基含有水性アクリル樹脂エマルション（Ａ−１）を得た。
Preparation 1 of a carboxyl group-containing aqueous acrylic resin (A)
In a separate flask equipped with a dropping funnel, thermometer, nitrogen inlet tube, reflux condenser and stirrer, 34.5 parts of ion-exchanged water, emulsifier (trade name “Perex SS-H”, manufactured by Kao Corporation, alkyl diphenyl ether sulfonic acid Sodium) 0.3 part was charged, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. After adding 0.6 parts of dodecyl mercaptan to a monomer mixture composed of 15 parts of styrene, 41.1 parts of 2-ethylhexyl acrylate, 42.0 parts of methyl methacrylate and 1.9 parts of acrylic acid, -H "1.2 parts in an aqueous emulsifier solution dissolved in 50 parts of ion-exchanged water, pre-emulsion obtained by emulsification using a mixer, and 0.3 part of ammonium persulfate dissolved in 13 parts of ion-exchanged water The initiator aqueous solution thus added was simultaneously dropped into the flask from a separate dropping funnel. The former was dropped evenly over 120 minutes and the latter over 150 minutes. After completion of the dropwise addition, the reaction was continued for an additional 120 minutes at the same temperature. After cooling, the solution was neutralized with ammonia water corresponding to 10 mol% of the acrylic acid used. The neutralized product was filtered through a 200-mesh wire mesh to obtain a carboxyl group-containing aqueous acrylic resin emulsion (A-1) having an acid value of 15 mg KOH / g, a glass transition temperature of 5 ° C., and a solid content of 50%.
製造例２
製造例１において、スチレン１５部、２−エチルヘキシルアクリレート４１．１部、メチルメタクリレート３３．６部及びアクリル酸１０．３部からなるモノマー混合液を用いた以外は、製造例１と同様にして、酸価８０ｍｇＫＯＨ／ｇ、ガラス転移温度５℃、固形分５０％のカルボキシル基含有水性アクリル樹脂エマルション（Ａ−２）を得た。
Production Example 2
In Production Example 1, except that a monomer mixed solution consisting of 15 parts of styrene, 41.1 parts of 2-ethylhexyl acrylate, 33.6 parts of methyl methacrylate and 10.3 parts of acrylic acid was used, in the same manner as in Production Example 1, A carboxyl group-containing aqueous acrylic resin emulsion (A-2) having an acid value of 80 mgKOH / g, a glass transition temperature of 5 ° C., and a solid content of 50% was obtained.
カルボキシル基含有変性澱粉（Ｂ）の調製
澱粉分子量の調整
変性澱粉の合成に使用する原料澱粉は、必要に応じて、以下の方法に準じて酸処理を行うことで分子量の調整を行った。原料澱粉を水に懸濁し４０％濃度のスラリーを調製した。これを約５０℃に保持して撹拝しながら所定量の塩酸を前記スラリーに添加した。前記塩酸の添加開始から所定時間上記温度で撹拝しながら保持し、酸処理を実施した。その後、前記スラリーを水酸化ナトリウム溶液でｐＨ６．５〜７に中和し、脱水、洗浄、乾燥させることで目的分子量の酸処理澱粉を得た。酸処理澱粉の分子量はＧＰＣ法にて測定した。
Preparation of carboxyl group-containing modified starch (B)
Adjustment of starch molecular weight The raw material starch used for the synthesis of the modified starch was subjected to acid treatment according to the following method, if necessary, to adjust the molecular weight. The raw material starch was suspended in water to prepare a 40% strength slurry. While maintaining this at about 50 ° C. and stirring, a predetermined amount of hydrochloric acid was added to the slurry. The acid treatment was carried out while stirring at the above temperature for a predetermined time from the start of addition of the hydrochloric acid. Thereafter, the slurry was neutralized with sodium hydroxide solution to pH 6.5-7, dehydrated, washed, and dried to obtain acid-treated starch having a target molecular weight. The molecular weight of the acid-treated starch was measured by GPC method.
製造例３
重量平均分子量約８０万の酸処理コーンスターチを、水に懸濁して３５％のスラリーを調製した。これを３０℃にセットした恒温槽中で撹拝しながら加温し、水酸化ナトリウムでｐＨを８．５に調整した。ｐＨを８．０〜８．５に維持しながら、前記コーンスターチに対して、６％の無水コハク酸を約３０分間かけて添加し、添加終了後さらに５分間反応させた。その後、塩酸を用いて反応液を中和し、これを５０％濃度のエタノール溶液に懸濁して脱水、洗浄し、乾燥させることで酸価２１．２ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−１）を得た。
Production Example 3
A 35% slurry was prepared by suspending acid-treated corn starch having a weight average molecular weight of about 800,000 in water. This was heated while stirring in a thermostat set at 30 ° C., and the pH was adjusted to 8.5 with sodium hydroxide. While maintaining the pH at 8.0 to 8.5, 6% succinic anhydride was added to the corn starch over about 30 minutes, and the reaction was further continued for 5 minutes. Thereafter, the reaction solution is neutralized with hydrochloric acid, suspended in a 50% ethanol solution, dehydrated, washed, and dried to obtain a carboxyl group-containing modified starch having an acid value of 21.2 mgKOH / g (B- 1) was obtained.
製造例４
重量平均分子量約１０万の酸処理コーンスターチを原料とし、無水コハク酸の添加率をコーンスターチに対して１０％とした以外は製造例３と同様にして、酸価３２．９ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−２）を得た。
Production Example 4
Contains a carboxyl group with an acid value of 32.9 mgKOH / g except that the raw material is acid-treated corn starch having a weight average molecular weight of about 100,000 and the addition rate of succinic anhydride is 10% with respect to corn starch. Modified starch (B-2) was obtained.
製造例５
重量平均分子量約５万の酸処理コーンスターチを原料とし、無水コハク酸の添加率をコーンスターチに対して１０％とした以外は製造例３と同様にして、酸価３４．３ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−３）を得た。
Production Example 5
Contains a carboxyl group having an acid value of 34.3 mgKOH / g in the same manner as in Production Example 3 except that acid-treated corn starch having a weight average molecular weight of about 50,000 is used as a raw material, and the addition rate of succinic anhydride is 10% with respect to corn starch. Modified starch (B-3) was obtained.
製造例６
重量平均分子量約１万の酸処理コーンスターチを原料とし、無水コハク酸の添加率をコーンスターチに対して１０％とした以外は製造例３と同様にして、酸価３５．６ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−４）を得た。
Production Example 6
Contains a carboxyl group with an acid value of 35.6 mgKOH / g in the same manner as in Production Example 3 except that acid-treated corn starch having a weight average molecular weight of about 10,000 is used as a raw material, and the addition rate of succinic anhydride is 10% with respect to corn starch. Modified starch (B-4) was obtained.
製造例７
重量平均分子量約１０万の酸処理コーンスターチを原料とし、無水コハク酸の添加率をコーンスターチに対して２８％とした以外は製造例３と同様にして、酸価７１．５ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−５）を得た。
Production Example 7
Contains a carboxyl group with an acid value of 71.5 mgKOH / g in the same manner as in Production Example 3, except that acid-treated corn starch having a weight average molecular weight of about 100,000 is used as a raw material and the addition rate of succinic anhydride is 28% with respect to corn starch. Modified starch (B-5) was obtained.
製造例８
重量平均分子量約１０万の酸処理ハイアミロースコーンスターチを原料とし、無水コハク酸の添加率をハイアミロースコーンスターチに対して１４％とした以外は製造例３と同様にして、酸価４７．４ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−６）を得た。
Production Example 8
Acid value 47.4 mgKOH / g in the same manner as in Production Example 3 except that acid-treated high amylose corn starch having a weight average molecular weight of about 100,000 was used as a raw material, and the addition rate of succinic anhydride was 14% with respect to high amylose corn starch. Of carboxyl group-containing modified starch (B-6) was obtained.
製造例９
重量平均分子量約５万の酸処理タピオカ澱粉を原料とし、無水コハク酸の添加率をタピオカ澱粉に対して１３％とした以外は製造例３と同様にして、酸価４３．２ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−７）を得た。
Production Example 9
A carboxylate having an acid value of 43.2 mgKOH / g was prepared in the same manner as in Production Example 3, except that acid-treated tapioca starch having a weight average molecular weight of about 50,000 was used as a raw material, and the addition rate of succinic anhydride was 13% with respect to tapioca starch. Group-containing modified starch (B-7) was obtained.
製造例１０
重量平均分子量約１０万の酸処理コーンスターチを水に懸濁して３５％濃度のスラリーを調製した。これを５０℃にセットした恒温槽中で撹拝しながら加温し、水酸化ナトリウムを前記コーンスターチに対して１６．８％添加し、澱粉を完全に糊化した。ここにモノクロロ酢酸ナトリウムを前記コーンスターチに対して４０％添加し、５時間反応させた。その後、塩酸で反応液を中和し、これを９９％濃度のエタノールに激しく撹拝しながら流し込み澱粉を沈澱させた。これを吸引ろ過して乾燥させることで、酸価６２．１ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−８）を得た。
Production Example 10
A 35% strength slurry was prepared by suspending acid-treated corn starch having a weight average molecular weight of about 100,000 in water. This was heated while stirring in a thermostat set at 50 ° C., and 16.8% of sodium hydroxide was added to the corn starch to completely gelatinize the starch. To this, sodium monochloroacetate (40%) was added to the corn starch and allowed to react for 5 hours. Thereafter, the reaction solution was neutralized with hydrochloric acid and poured into 99% ethanol with vigorous stirring to precipitate starch. This was suction filtered and dried to obtain a carboxyl group-containing modified starch (B-8) having an acid value of 62.1 mgKOH / g.
製造例１１
未処理コーンスターチを水に懸濁し４０％濃度のスラリーを調製した。これを４０℃にセットした恒温槽中で撹拝しながら加温し、水酸化ナトリウムを添加してｐＨを９．０に調整した。ｐＨを９．０に維持しながら前記コーンスターチに対して４．８％の次亜塩素酸ナトリウム溶液（有効塩素：１２．３６％、水酸化ナトリウム：０．４２％）を約９０分間かけて添加し、その後１５０分間反応させた。その後、残留する塩素を亜硫酸水素ナトリウムで消塩し、塩酸で中和した後、脱水、洗浄し、乾燥させることで、重量平均分子量３０万、酸価１２．５ｍｇＫＯＨ／ｇのカルボキシル基含有変性澱粉（Ｂ−９）を得た。
Production Example 11
Untreated corn starch was suspended in water to prepare a 40% strength slurry. This was heated while stirring in a thermostat set at 40 ° C., and sodium hydroxide was added to adjust the pH to 9.0. 4.8% sodium hypochlorite solution (effective chlorine: 12.36%, sodium hydroxide: 0.42%) was added to the corn starch over about 90 minutes while maintaining the pH at 9.0. And then allowed to react for 150 minutes. Then, the residual chlorine is demineralized with sodium bisulfite, neutralized with hydrochloric acid, dehydrated, washed, and dried, so that the carboxyl group-containing modified starch having a weight average molecular weight of 300,000 and an acid value of 12.5 mgKOH / g (B-9) was obtained.
表１に、製造例３〜１１で得られたカルボキシル基含有変性澱粉（Ｂ−１）〜（Ｂ−９）の原料、原料調製時の酸処理ＨＣｌ添加率、重量平均分子量、変性方法、及び酸価を示す。 In Table 1, the raw material of the carboxyl group-containing modified starch (B-1) to (B-9) obtained in Production Examples 3 to 11, the acid-treated HCl addition rate at the time of raw material preparation, the weight average molecular weight, the modification method, and Indicates the acid value.
カルボキシル基含有変性澱粉（Ｂ−１）〜（Ｂ―７）、（Ｂ−９）の糊化
温度２５℃のイオン交換水７０部に、各変性澱粉３０部を混合・撹拝させスラリー化した後、温度９５℃に昇温させ、この温度を保ったまま３０分間攪拌した。その後、３０℃まで冷却後、アンモニア水を用いてｐＨ７〜８に調整し、固形分３０％の糊化した各変性澱粉（Ｂ−１）〜（Ｂ−７）、（Ｂ−９）を得た。これらを用いて塗料化を行った。
30 parts of each modified starch was mixed and stirred in 70 parts of ion-exchanged water having a gelatinization temperature of 25 ° C. of carboxyl group-containing modified starches (B-1) to (B-7) and (B-9) to form a slurry. Thereafter, the temperature was raised to 95 ° C., and the mixture was stirred for 30 minutes while maintaining this temperature. Then, after cooling to 30 ° C., the pH is adjusted to 7 to 8 using aqueous ammonia, and gelatinized modified starches (B-1) to (B-7) and (B-9) having a solid content of 30% are obtained. It was. These were used to make a paint.
カルボキシル基含有変性澱粉（Ｂ−８）の糊化
温度２５℃のイオン交換水７０部を準備し、これを激しく攪拌しながらカルボキシル基含有変性澱粉（Ｂ−８）３０部を少しずつ添加していき、３０分間攪拌を続けることで完全に溶解させた。その後、アンモニア水を用いてｐＨ７〜８に調整し、固形分３０％の糊化した変性澱粉（Ｂ−８）を得た。これを用いて塗料化を行った。
70 parts of ion-exchanged water having a gelatinization temperature of 25 ° C. of carboxyl group-containing modified starch (B-8) was prepared, and 30 parts of carboxyl group-containing modified starch (B-8) was added little by little while stirring vigorously. The solution was completely dissolved by continuing stirring for 30 minutes. Then, it adjusted to pH 7-8 using aqueous ammonia, and gelatinized modified starch (B-8) with a solid content of 30% was obtained. This was used to make a paint.
顔料ペーストの調製
製造例１２
イオン交換水６部、増粘剤（商品名「ＳＰ−６００Ｎ」、ダイセル化学工業社製、ヒドロキシエチルセルロース系増粘剤）０．１部、顔料分散剤（商品名「Ｄｉｓｐｅｒｂｙｋ−１９０」、ビッグケミー社製）１．５部、二酸化チタン（商品名「ＴＩ−ＰＵＲＥ Ｒ−７０６」、デュポン社製）２２．２部、工業用防腐剤（商品名「ベストサイド２０１」、日本曹達社製）０．１部、及び消泡剤（商品名「ＢＹＫ−０１８」、ビッグケミー社製）０．１部を、ステンレス容器に入れて混合後、ガラスビーズを投入し、ディスパーにて３０分間攪拌・分散させて、顔料ペーストＩを得た。
Preparation Example 12 of Pigment Paste
6 parts ion-exchanged water, 0.1 part thickener (trade name “SP-600N”, manufactured by Daicel Chemical Industries, Ltd., hydroxyethyl cellulose-based thickener), pigment dispersant (trade name “Disperbyk-190”, Big Chemie 1.5 parts, titanium dioxide (trade name “TI-PURE R-706”, manufactured by DuPont) 22.2 parts, industrial preservative (trade name “Best Side 201”, manufactured by Nippon Soda Co., Ltd.) 1 part and 0.1 part of an antifoaming agent (trade name “BYK-018”, manufactured by Big Chemie) are placed in a stainless steel container and mixed, then glass beads are added, and stirred and dispersed with a disper for 30 minutes. Pigment paste I was obtained.
実施例１〜１５
後記の表２及び表３に示す配合組成で、本発明の水性塗料組成物を調製した。即ち、まず、硬化剤（Ｃ）以外の各成分をディスパーにて３０分間混合・攪拌した後、硬化剤（Ｃ）を添加し、更に１０分間攪拌を行うことにより、水性塗料組成物を調製した。
Examples 1-15
The aqueous coating composition of the present invention was prepared with the blending composition shown in Tables 2 and 3 below. That is, first, after mixing and stirring each component other than the curing agent (C) with a disper for 30 minutes, the curing agent (C) was added, and stirring was further performed for 10 minutes to prepare an aqueous coating composition. .
実施例１〜１１及び１３〜１５の硬化剤（Ｃ）としては、カルボジイミド化合物である「カルボジライトＶ−０２−Ｌ２」（商品名、日清紡（株）製、カルボジイミド基含有化合物水溶液、固形分４０％、カルボジイミド当量３８５）（Ｃ−１）を、（Ａ）成分及び（Ｂ）成分の合計カルボキシル基１当量に対して、実施例１〜１１及び１３ではカルボジイミド基が１当量になる量、実施例１４及び１５ではカルボジイミド基が０．１当量になる量、それぞれ配合した。 Examples of the curing agents (C) of Examples 1 to 11 and 13 to 15 include “carbodilite V-02-L2” (trade name, manufactured by Nisshinbo Co., Ltd., carbodiimide group-containing compound aqueous solution, solid content 40%. , Carbodiimide equivalent 385) (C-1) with respect to 1 equivalent of the total carboxyl group of component (A) and component (B), in Examples 1-11 and 13, the amount that the carbodiimide group becomes 1 equivalent, Example In Nos. 14 and 15, the carbodiimide groups were blended in amounts of 0.1 equivalent.
また、実施例１２の硬化剤（Ｃ）としては、オキサゾリン化合物である「エポクロスＷＳ−７００」（商品名、日本触媒（株）製、オキサゾリン基含有アクリル樹脂水溶液、固形分２５％、オキサゾリン価２２０）（Ｃ−２）を、（Ａ）成分及び（Ｂ）成分の合計カルボキシル基１当量に対して、オキサゾリン基が１当量になる量配合した。 Further, as the curing agent (C) of Example 12, “Epocross WS-700” (trade name, manufactured by Nippon Shokubai Co., Ltd., oxazoline group-containing acrylic resin aqueous solution, solid content 25%, oxazoline value 220, which is an oxazoline compound. ) (C-2) was blended in such an amount that the oxazoline group was 1 equivalent with respect to 1 equivalent of the total carboxyl group of the components (A) and (B).
表２及び表３に、実施例１〜１５の水性塗料組成物の配合組成、（Ａ）成分及び（Ｂ）成分の固形分比を示す。 Tables 2 and 3 show the composition ratios of the aqueous coating compositions of Examples 1 to 15, and the solid content ratios of the component (A) and the component (B).
表２及び表３において、配合組成の数値は、部を示す。また、注は、以下のものを示す。 In Table 2 and Table 3, the numerical value of a compound composition shows a part. The note indicates the following.
（注１）造膜助剤：商品名「ＣＳ−１２」、チッソ社製、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 (Note 1) Film-forming aid: Trade name “CS-12”, manufactured by Chisso Corporation, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate
（注２）ｐＨ調整剤：２５％アンモニア水、和光純薬社製 (Note 2) pH adjuster: 25% ammonia water, manufactured by Wako Pure Chemical Industries, Ltd.
（注３）消泡剤：商品名「ＢＹＫ−０２４」、ビッグケミー社製 (Note 3) Antifoaming agent: trade name “BYK-024”, manufactured by Big Chemie
（注４）増粘剤１：商品名「アデカノールＵＨ−４２０」、旭電化社製、ウレタン会合型増粘剤 (Note 4) Thickener 1: Trade name “Adecanol UH-420”, manufactured by Asahi Denka Co., Ltd., urethane associative thickener
（注５）増粘剤２：商品名「プライマルＴＴ−６１５」、ローム・アンド・ハース社製、アルカリ膨潤型増粘剤 (Note 5) Thickener 2: Trade name “Primal TT-615”, manufactured by Rohm and Haas, alkali swelling type thickener
比較例１
カルボキシル基含有水性樹脂（Ａ）を配合せず、カルボキシル基含有変性澱粉（Ｂ−１）の配合量を８２．４部とし、「カルボジライトＶ−０２−Ｌ２」（Ｃ−１）の配合量を９．０部（カルボキシル基１当量に対しカルボジイミド基１当量）とした以外は、実施例１と同様にして、比較用の水性塗料組成物を調製した。
Comparative Example 1
The amount of the carboxyl group-containing modified starch (B-1) is 82.4 parts, and the amount of “Carbodilite V-02-L2” (C-1) is not blended with the carboxyl group-containing aqueous resin (A). A comparative water-based coating composition was prepared in the same manner as in Example 1 except that 9.0 parts (1 equivalent of carbodiimide group per 1 equivalent of carboxyl group) was used.
比較例２
硬化剤を、カルボジイミド化合物からイソシアネート化合物に変更したこと以外は、実施例１と同様にして、比較用の水性塗料組成物を調製した。硬化剤のイソシアネート化合物としては、「バーノックＤＮＷ−５０００」（商品名、大日本インキ化学工業（株）製、水分散型ポリイソシアネート架橋剤）を、変性澱粉（Ｂ−１）が有する水酸基に基づく水酸基価９７８ｍｇＫＯＨ／ｇから計算して、（Ｂ−１）の水酸基１当量に対しイソシアネート基が１当量になる量である６７．０部配合した。
Comparative Example 2
An aqueous coating composition for comparison was prepared in the same manner as in Example 1 except that the curing agent was changed from the carbodiimide compound to the isocyanate compound. As the isocyanate compound of the curing agent, “Bernock DNW-5000” (trade name, manufactured by Dainippon Ink & Chemicals, Inc., water-dispersed polyisocyanate crosslinking agent) is based on the hydroxyl group of the modified starch (B-1). Calculated from a hydroxyl value of 978 mgKOH / g, 67.0 parts were blended in such an amount that the isocyanate group was 1 equivalent with respect to 1 equivalent of the hydroxyl group of (B-1).
次に、実施例及び比較例で得られた各水性塗料組成物について、塗膜性能（塗膜外観、耐水性、耐アルカリ性、耐洗浄性及び促進耐候性）を調べた。尚、耐洗浄性は、耐摩耗性の指標として調べた。試験方法は、以下の通りである。 Next, the coating performance (coating appearance, water resistance, alkali resistance, washing resistance and accelerated weather resistance) of each aqueous coating composition obtained in Examples and Comparative Examples was examined. The washing resistance was examined as an index of wear resistance. The test method is as follows.
塗膜外観：フレキシブル板（ＪＩＳ Ａ ５４３０準拠）に、「ニッペウルトラシーラーIII(日本ペイント（株）製、カルボキシル基含有スチレン−アクリル樹脂系シーラー)を塗付け量１００ｇ／ｍ２で刷毛を用いて塗装し、１６時間放置(温度２３℃湿度５０％)後、評価塗料を塗付け量１００ｇ／ｍ２で刷毛を用いて塗装間隔時間３時間で、２回塗り重ね塗布した（塗付け量合計２００ｇ／ｍ２）。その後、２４時間放置して、塗膜表面の状態を観察し、下記基準により、目視で評価した。
○：塗膜に異常が認められない。
×：割れ、ちぢみ、ピンホールなどの異常が認められる。
Appearance of coating film: “Nippe Ultra Sealer III (manufactured by Nippon Paint Co., Ltd., carboxyl group-containing styrene-acrylic resin sealer)” was applied to a flexible board (JIS A 5430 compliant) using a brush at a coating amount of 100 g / m 2. After coating and leaving for 16 hours (temperature 23 ° C., humidity 50%), the evaluation paint was applied twice with a brush at a coating amount of 100 g / m 2 and a coating interval time of 3 hours (total coating amount 200 g). / M 2 ) After that, the film was left for 24 hours, the state of the coating film surface was observed, and visually evaluated according to the following criteria.
○: No abnormality is observed in the coating film.
X: Abnormalities such as cracks, itchiness and pinholes are observed.
耐水性：フレキシブル板（ＪＩＳ Ａ ５４３０準拠）に、「ニッペウルトラシーラーIII(日本ペイント（株）製、カルボキシル基含有スチレン−アクリル樹脂系シーラー)を塗付け量１００ｇ／ｍ２で刷毛を用いて塗装し、１６時間放置(温度２３℃湿度５０％)後、評価塗料を塗付け量１００ｇ／ｍ２で刷毛を用いて塗装間隔時間３時間で、２回塗り重ね塗布した（塗付け量合計２００ｇ／ｍ２）。その後、７日間乾燥養生して耐水性試験板を作成し、２０℃の水に７日間没水した。取り出して水洗後３０分以内に、塗膜表面の状態を観察し、下記基準により、目視で評価した。
◎：水に浸した塗膜に膨れ、割れ、剥がれ等がない。
○：水に浸した塗膜面積３％未満に膨れ、割れ、剥がれ等がある。
△：水に浸した塗膜面積３％以上１０％未満に膨れ、割れ、剥がれ等がある。
×：水に浸した塗膜面積１０％以上３０％未満に膨れ、割れ、剥がれ等がある。
××：水に浸した塗膜面積３０％以上に膨れ、割れ、剥がれ等がある。
Water resistance: “Nippe Ultra Sealer III (manufactured by Nippon Paint Co., Ltd., carboxyl group-containing styrene-acrylic resin-based sealer) is applied to a flexible board (JIS A 5430 compliant) with a brush at a coating amount of 100 g / m 2. After standing for 16 hours (temperature 23 ° C., humidity 50%), the evaluation paint was applied twice with a brush at a coating amount of 100 g / m 2 and a coating interval time of 3 hours (total coating amount 200 g / m 2 ). m 2 ) After that, it was dried and cured for 7 days to prepare a water resistance test plate, and submerged in water at 20 ° C. for 7 days. Visual evaluation was made according to the criteria.
(Double-circle): There is no swelling, a crack, peeling, etc. in the coating film immersed in water.
◯: Swelling, cracking, peeling, etc. occur when the coating area immersed in water is less than 3%.
(Triangle | delta): There exists a swelling, a crack, peeling, etc. to the coating-film area 3% or more and less than 10% immersed in water.
X: The coating film area soaked in water swells to 10% or more but less than 30%, cracks, peels off, and the like.
XX: Swelled, cracked, peeled, etc. to a coating area of 30% or more immersed in water.
耐アルカリ性：フレキシブル板（ＪＩＳ Ａ ５４３０準拠）に、「ニッペウルトラシーラーIII(日本ペイント（株）製、カルボキシル基含有スチレン−アクリル樹脂系シーラー)を塗付け量１００ｇ／ｍ２で刷毛を用いて塗装し、１６時間放置(温度２３℃湿度５０％)後、評価塗料を塗付け量１００ｇ／ｍ２で刷毛を用いて塗装間隔時間３時間で、２回塗り重ね塗布した（塗付け量合計２００ｇ／ｍ２）。その後、７日間乾燥養生して耐アルカリ性試験板を作成し、２０℃の水酸化ナトリウム３％水溶液に７日間没水した。取り出して水洗後３０分以内に、塗膜表面の状態を観察し、下記基準により、目視で評価した。
◎：塗膜に膨れ、割れ、剥がれ等がない。
○：塗膜面積３％未満に膨れ、割れ、剥がれ等がある。
△：塗膜面積３％以上１０％未満に膨れ、割れ、剥がれ等がある。
×：塗膜面積１０％以上３０％未満に膨れ、割れ、剥がれ等がある。
××：塗膜面積３０％以上に膨れ、割れ、剥がれ等がある。
Alkali resistance: “Nippe Ultra Sealer III (manufactured by Nippon Paint Co., Ltd., carboxyl group-containing styrene-acrylic resin-based sealer)” is applied to a flexible board (JIS A 5430 compliant) with a brush at a coating amount of 100 g / m 2. After standing for 16 hours (temperature 23 ° C., humidity 50%), the evaluation paint was applied twice with a brush at a coating amount of 100 g / m 2 and a coating interval time of 3 hours (total coating amount 200 g / m 2 ). m 2 ) After that, it was dried and cured for 7 days to prepare an alkali resistance test plate and submerged in a 3% aqueous solution of sodium hydroxide at 20 ° C. for 7 days. Was visually evaluated according to the following criteria.
(Double-circle): There is no swelling, a crack, peeling, etc. to a coating film.
◯: Swelling, cracking, peeling, etc. occur when the coating area is less than 3%.
Δ: Swells, cracks, peels off, etc. when the coating area is 3% or more and less than 10%.
X: Swelling, cracking, peeling, etc. occur in the coating film area of 10% or more and less than 30%.
XX: Swells, cracks, peels, etc. over 30% coating area.
耐洗浄性：ＪＩＳ Ｋ ５６６０に規定されるつや合成樹脂エマルションペイント規格に従って、調べた。装置としては、ＪＩＳ Ｋ ５６００−５−１１の６．３の湿潤磨耗試験装置の機能をもち、試験槽、石けん液槽、ブラシなどから構成され、試験片の塗膜上をブラシが往復するものを用いた。試験片は、硬質塩化ビニルシート(ＪＩＳ Ｋ ６７３４に規定)に、評価塗料を６milアプリケーターを用いて塗布し、7日間乾燥養生して耐洗浄性試験板を作成した。 Washing resistance: Investigated according to the glossy synthetic resin emulsion paint standard defined in JIS K 5660. The equipment has the function of 6.3 wet abrasion test equipment of JIS K 5600-5-11, and consists of a test tank, a soap bath, a brush, etc., and the brush reciprocates on the coating film of the test piece. Was used. The test piece was applied to a hard vinyl chloride sheet (specified in JIS K 6734) with an evaluation paint using a 6 mil applicator and dried and cured for 7 days to prepare a wash resistance test plate.
耐洗浄性試験は、ＪＩＳ Ｋ ５６６０の６．１３の規定に沿って、次のようにして、行った。即ち、試験片を、洗浄性試験装置の試験槽の試験台に、塗面を上向きにして水平に固定する。０．５％石けん水溶液を十分に浸み込ませたブラシを試験片の塗面に載せ、こする面に０．５％石けん水溶液を滴下し、常にぬれた状態に保ちながら、塗面をブラシで１０００回往復させ、こする。その後、試験片を取り出し水で洗い、乾燥させた後、塗膜表面の状態を観察し、下記基準により、目視で評価した。
○：ブラシの往復回数１０００回で、こすった箇所に塗膜の破れ、磨耗による素地の露出が認められない。
×：ブラシの往復回数１０００回で、こすった箇所に塗膜の破れ、磨耗による素地の露出が認められる。
The washing resistance test was performed as follows in accordance with the provisions of JIS K 5660, 6.13. That is, the test piece is fixed horizontally on the test stand of the test tank of the detergency test apparatus with the coating surface facing upward. Place a brush thoroughly soaked with 0.5% soap solution on the coated surface of the test piece, drop 0.5% soap solution on the surface to be rubbed, and keep the wet surface while always brushing the painted surface. And then rub 1000 times. Thereafter, the test piece was taken out, washed with water and dried, and then the state of the coating film surface was observed and visually evaluated according to the following criteria.
○: The brush was reciprocated 1000 times, and the paint film was not torn in the rubbed area, and the substrate was not exposed due to wear.
X: The number of reciprocations of the brush was 1000, and the paint film was torn in the rubbed area and the substrate was exposed due to wear.
促進耐候性：フレキシブル板（ＪＩＳ Ａ ５４３０準拠）に、「ニッペウルトラシーラーIII(日本ペイント（株）製、カルボキシル基含有スチレン−アクリル樹脂系シーラー)を塗付け量１００ｇ／ｍ２で刷毛を用いて塗装し、１６時間放置(温度２３℃湿度５０％)後、評価塗料を塗付け量１００ｇ／ｍ２で刷毛を用いて塗装間隔時間３時間で、２回塗り重ね塗布した（塗付け量合計２００ｇ／ｍ２）。その後、７日間乾燥養生して促進耐候性試験板を作成し、ＪＩＳ Ｋ ５６００−７−７に規定されるキセノンランプ法により、照射４８０時間経過後に試験体を取り出し室内に１時間放置した後、塗膜表面の状態を観察し、下記基準により、目視で評価した。下記基準において、白亜化等級は、ＪＩＳ Ｋ ５６００−８−６の規定による。
○：白亜化等級が１以下で、膨れ、はがれ、割れ等がなく、色の変化が見本板と比較して大きな変化がない。
×：白亜化等級が２以上であるか、又は、はがれ、割れが発生し、又は、色の変化が大きい。
Accelerated weather resistance: “Nippe Ultra Sealer III (manufactured by Nippon Paint Co., Ltd., carboxyl group-containing styrene-acrylic resin-based sealer) is applied to a flexible board (JIS A 5430 compliant) using a brush at a coating amount of 100 g / m 2. After coating and leaving for 16 hours (temperature 23 ° C., humidity 50%), the evaluation paint was applied twice with a brush at a coating amount of 100 g / m 2 and a coating interval time of 3 hours (total coating amount 200 g). / M 2 ) Thereafter, an accelerated weathering test plate was prepared by drying and curing for 7 days, and the test specimen was taken out after 480 hours of irradiation according to the xenon lamp method specified in JIS K 5600-7-7. After being allowed to stand for a period of time, the state of the coating film surface was observed and visually evaluated according to the following criteria, where the chalking grade was in accordance with the provisions of JIS K 5600-8-6.
○: Chalkification grade is 1 or less, there is no swelling, peeling, cracking, etc., and there is no significant change in color compared to the sample board.
X: chalking grade is 2 or more, or peeling, cracking occurs, or color change is large.
試験結果を表４及び表５に示した。 The test results are shown in Tables 4 and 5.
Claims (8)
（Ｂ）カルボキシル基含有変性澱粉、及び
（Ｃ）カルボキシル基と硬化反応する官能基を有する硬化剤
を含有し、
前記水性樹脂（Ａ）はカルボキシル基含有水性アクリル樹脂からなる
水性塗料組成物。 (A) a carboxyl group-containing aqueous resin,
(B) a carboxyl group-containing modified starch, and (C) a curing agent having a functional group that undergoes a curing reaction with the carboxyl group ,
The aqueous resin composition (A) comprises a carboxyl group-containing aqueous acrylic resin .
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