JP2016069618A - Aqueous coating composition - Google Patents
Aqueous coating composition Download PDFInfo
- Publication number
- JP2016069618A JP2016069618A JP2014242770A JP2014242770A JP2016069618A JP 2016069618 A JP2016069618 A JP 2016069618A JP 2014242770 A JP2014242770 A JP 2014242770A JP 2014242770 A JP2014242770 A JP 2014242770A JP 2016069618 A JP2016069618 A JP 2016069618A
- Authority
- JP
- Japan
- Prior art keywords
- water
- resin
- cellulose
- coating composition
- mass
- 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.)
- Pending
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 57
- 229920002678 cellulose Polymers 0.000 claims abstract description 46
- 239000001913 cellulose Substances 0.000 claims abstract description 46
- 239000000835 fiber Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 238000006467 substitution reaction Methods 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 239000003086 colorant Substances 0.000 claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 238000000518 rheometry Methods 0.000 abstract description 8
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000006185 dispersion Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- 239000000049 pigment Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 9
- -1 hydroxyethyl group Chemical group 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 7
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000007665 sagging Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- COQLPRJCUIATTQ-UHFFFAOYSA-N Uranyl acetate Chemical compound O.O.O=[U]=O.CC(O)=O.CC(O)=O COQLPRJCUIATTQ-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000003405 preventing effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- GUYIZQZWDFCUTA-UHFFFAOYSA-N (pentadecachlorophthalocyaninato(2-))-copper Chemical compound [Cu+2].N1=C([N-]2)C3=C(Cl)C(Cl)=C(Cl)C(Cl)=C3C2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC2=C(C(Cl)=C(C(Cl)=C3)Cl)C3=C1[N-]2 GUYIZQZWDFCUTA-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241001437124 Atanus Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- UAHZTKVCYHJBJQ-UHFFFAOYSA-N [P].S=O Chemical compound [P].S=O UAHZTKVCYHJBJQ-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、水系塗料組成物に関するものである。 The present invention relates to a water-based coating composition.
従来、水系塗料のレオロジーコントロール剤としては、合成系および天然系の高分子が使用されてきた。安全性や環境に対する配慮から、天然系の高分子が好まれる傾向にある。天然系の高分子としては、セルロースおよびセルロースの誘導体が使用されている。従来の水系塗料組成物としては、レオロジーコントロール剤として水溶性セルロースエーテルを用いる水系塗料組成物が開示されている（特許文献１）。さらに、繊維径が１０μｍ以下の微細セルロースを用いる水系塗料組成物が開示されている（特許文献２）。 Conventionally, synthetic and natural polymers have been used as rheology control agents for water-based paints. Natural polymers tend to be preferred for safety and environmental considerations. Cellulose and cellulose derivatives are used as natural polymers. As a conventional water-based coating composition, a water-based coating composition using a water-soluble cellulose ether as a rheology control agent is disclosed (Patent Document 1). Furthermore, an aqueous coating composition using fine cellulose having a fiber diameter of 10 μm or less is disclosed (Patent Document 2).
しかし、水溶性セルロースエーテルは水溶性であるため、水系塗料組成物から得られる塗膜の耐水性を低下させるという問題があった（特許文献１）。一方、特許文献２に開示された微細セルロースは水溶性ではないため、水溶性セルロースエーテルのような問題は解消される。しかし、セルロースを微細化するには、多大なエネルギーとコストが必要である。セルロースは、ミクロフィブリルと呼ばれるナノファイバーが繊維方向に集束してより大きな単位の繊維を形成しており、セルロース分子間およびナノファイバー表面間で主に水素結合によって強く集束しているからである。 However, since water-soluble cellulose ether is water-soluble, there has been a problem that the water resistance of a coating film obtained from an aqueous coating composition is lowered (Patent Document 1). On the other hand, since the fine cellulose disclosed in Patent Document 2 is not water-soluble, problems such as water-soluble cellulose ether are solved. However, enormous energy and cost are required to refine cellulose. This is because, in cellulose, nanofibers called microfibrils are focused in the fiber direction to form larger units of fibers, and are strongly focused mainly by hydrogen bonds between cellulose molecules and between nanofiber surfaces.
このような理由から、従来の微細セルロースは、ミクロフィブリルと呼ばれるナノファイバーにまで完全に微細化されていないため、レオロジーコントロール剤としての粘度発現が不十分であり、添加量を多くしなければならないという問題があった。このことから、水系塗料組成物のレオロジーコントロール剤として、塗膜の耐水性を低下させることがなく、少量の添加で効果を発現するセルロース系のレオロジーコントロール剤が求められていた。 For these reasons, the conventional fine cellulose has not been completely refined to nanofibers called microfibrils, so that the viscosity expression as a rheology control agent is insufficient and the addition amount must be increased. There was a problem. For this reason, there has been a demand for a cellulose-based rheology control agent that does not lower the water resistance of the coating film and exhibits an effect when added in a small amount, as a rheology control agent for water-based coating compositions.
本発明は、このような事情に鑑みてなされたもので、少量で効果を発現するレオロジーコントロール剤により塗膜の耐水性に優れた水系塗料組成物を提供することを目的とする。 This invention is made | formed in view of such a situation, and it aims at providing the water-based coating composition excellent in the water resistance of the coating film with the rheology control agent which expresses an effect in a small quantity.
すなわち、本発明は下記に掲げる発明に関する。
〔１〕数平均繊維径が２ｎｍ以上５００ｎｍ以下のセルロース繊維であって、セルロース分子中の水酸基に置換基が導入されており、置換度が０．０１以上０．５以下であり、Ｉ型及び／又はＩＩ型の結晶構造を有し、アスペクト比が５０以上であるセルロース繊維、水系樹脂、及び着色剤を含有する水系塗料組成物。
〔２〕好ましい実施形態として上記水系樹脂が、アクリル系樹脂、アルキド系樹脂、ポリエステル系樹脂、ポリウレタン樹脂、アクリルウレタン樹脂、ブロックイソシアネート含有化合物、フッ素樹脂、エポキシ樹脂、エポキシアクリレート樹脂、フェノール樹脂、メラミン樹脂、ビニル系樹脂、ポリアミド樹脂、及びセルロース系樹脂から選択される、１種又は２種以上である水系塗料組成物。
〔３〕好ましい実施形態として、上記セルロース繊維の含有量が０．０１質量％以上３質量％以下、上記水系樹脂の含有量が樹脂固形部として０質量％以上８０質量％以下、上記着色料の含有量が０質量％以上８０質量％以下である水系塗料組成物。
That is, this invention relates to the invention hung up below.
[1] Cellulose fibers having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced into the hydroxyl group in the cellulose molecule, the degree of substitution is 0.01 or more and 0.5 or less, A water-based paint composition containing cellulose fibers having a crystal structure of // type II and an aspect ratio of 50 or more, a water-based resin, and a colorant.
[2] As a preferred embodiment, the water-based resin is an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, an acrylic urethane resin, a blocked isocyanate-containing compound, a fluorine resin, an epoxy resin, an epoxy acrylate resin, a phenol resin, or a melamine. A water-based coating composition that is one or more selected from resins, vinyl resins, polyamide resins, and cellulose resins.
[3] As a preferred embodiment, the content of the cellulose fiber is 0.01% by mass or more and 3% by mass or less, and the content of the aqueous resin is 0% by mass or more and 80% by mass or less as a resin solid part. A water-based paint composition having a content of 0 to 80% by mass.
本発明の水系塗料組成物は、上記セルロース繊維が低濃度であっても高い粘性とチキソトロピーインデックスを示すため、従来の微細セルロースより少量でレオロジーコントロール効果を発揮する。さらに、塗料製造時の顔料分散性、塗料保管時の沈降・分離防止効果、沈降した顔料の再分散性、塗料のタレ防止効果に優れている。
また、上記セルロース繊維の分散物は水に溶解しないため、塗料塗膜の耐水性を低下させる恐れがない。
Since the water-based coating composition of the present invention exhibits a high viscosity and a thixotropy index even when the cellulose fiber is in a low concentration, it exhibits a rheology control effect in a smaller amount than conventional fine cellulose. Furthermore, it is excellent in pigment dispersibility during coating production, sedimentation / separation preventing effect during coating storage, redispersibility of precipitated pigment, and sagging preventing effect of the coating.
Further, since the cellulose fiber dispersion does not dissolve in water, there is no risk of reducing the water resistance of the paint film.
次に、本発明の実施の形態を詳しく説明する。 Next, embodiments of the present invention will be described in detail.
本発明の水系塗料組成物は上記特定のセルロース繊維、水系樹脂、着色剤及び水を用いて得ることができる。 The water-based coating composition of the present invention can be obtained using the specific cellulose fiber, water-based resin, colorant and water.
本発明のセルロース繊維は、数平均繊維径が２ｎｍ以上５００ｎｍ以下であって、セルロース分子中の水酸基に置換基が導入されており、置換度が０．０１以上０．５以下であり、Ｉ型及び／又はＩＩ型の結晶構造を有し、アスペクト比５０以上である
上記数平均繊維径は２ｎｍ以上５００ｎｍ以下、より好ましくは２ｎｍ以上１５０ｎｍ以下である。数平均繊維径が２ｎｍ未満であると、本質的に分散媒体に溶解してしまい、逆に数平均繊維径が５００ｎｍを超えると、セルロース繊維そのものの分散安定性が低下するため、機能を発現しない。
The cellulose fiber of the present invention has a number average fiber diameter of 2 nm or more and 500 nm or less, a substituent is introduced into the hydroxyl group in the cellulose molecule, the degree of substitution is 0.01 or more and 0.5 or less, type I The number average fiber diameter having an II type crystal structure and an aspect ratio of 50 or more is 2 nm or more and 500 nm or less, more preferably 2 nm or more and 150 nm or less. If the number average fiber diameter is less than 2 nm, it is essentially dissolved in the dispersion medium. Conversely, if the number average fiber diameter exceeds 500 nm, the dispersion stability of the cellulose fiber itself is lowered, so that no function is exhibited. .
ここで、上記数平均繊維径の解析は、例えば、次のようにして行うことができる。すなわち、固形分率で０．０５〜０．１質量％のセルロース繊維の水分散体を調製し、その分散体を、親水化処理済みのカーボン膜被覆グリッド上にキャストして、透過型電子顕微鏡（ＴＥＭ）の観察用試料とする。なお、本発明外の大きな繊維径の繊維を含む場合には、ガラス上へキャストした表面の走査型電子顕微鏡（ＳＥＭ）像を観察してもよい。そして、構成する繊維の大きさに応じて５０００倍、１００００倍あるいは５００００倍のいずれかの倍率で電子顕微鏡画像による観察を行う。その際に、得られた画像内に縦横任意の画像幅の軸を想定し、その軸に対し、２０本以上の繊維が交差するよう、試料および観察条件（倍率等）を調節する。そして、この条件を満たす観察画像を得た後、この画像に対し、１枚の画像当たり縦横２本ずつの無作為な軸を引き、軸に交錯する繊維の繊維径を目視で読み取っていく。このようにして、最低３枚の重複しない表面部分の画像を、電子顕微鏡で撮影し、各々２つの軸に交錯する繊維の繊維径の値を読み取る（したがって、最低２０本×２×３＝１２０本の繊維径の情報が得られる）。このようにして得られた繊維径のデータにより、数平均繊維径を算出する。 Here, the analysis of the said number average fiber diameter can be performed as follows, for example. Specifically, an aqueous dispersion of cellulose fibers having a solid content of 0.05 to 0.1% by mass was prepared, and the dispersion was cast on a carbon film-coated grid that had been subjected to a hydrophilic treatment, and a transmission electron microscope. (TEM) observation sample. In addition, when the fiber of the big fiber diameter outside this invention is included, you may observe the scanning electron microscope (SEM) image of the surface cast on glass. Then, observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times, or 50000 times depending on the size of the constituent fibers. At that time, an axis having an arbitrary vertical and horizontal image width is assumed in the obtained image, and the sample and observation conditions (magnification, etc.) are adjusted so that 20 or more fibers intersect the axis. Then, after obtaining an observation image that satisfies this condition, two random axes, vertical and horizontal, per image are drawn on this image, and the fiber diameter of the fiber that intersects the axis is visually read. In this way, images of at least three non-overlapping surface portions are taken with an electron microscope, and the fiber diameter values of the fibers intersecting with each of the two axes are read (thus, at least 20 × 2 × 3 = 120). Information on the fiber diameter of the book is obtained). The number average fiber diameter is calculated from the fiber diameter data thus obtained.
上記置換基としては、セルロース分子中の水酸基との間にエーテル結合が生じる置換基であれば特に制限されない。具体的には、カルボキシメチル基、メチル基、エチル基、シアノエチル基、ヒドロキシエチル基、ヒドロキシプロピル基、エチルヒドロキシエチル基、ヒドロキシプロピルメチル基等があげられる。これらのうち、カルボキシメチル基が好ましい。 The substituent is not particularly limited as long as it is a substituent that generates an ether bond with a hydroxyl group in the cellulose molecule. Specific examples include carboxymethyl group, methyl group, ethyl group, cyanoethyl group, hydroxyethyl group, hydroxypropyl group, ethylhydroxyethyl group, hydroxypropylmethyl group and the like. Of these, a carboxymethyl group is preferred.
上記置換度は、無水グルコース単位１モル当たりの置換基のモル数の平均値を表している。 The degree of substitution represents the average value of the number of moles of substituents per mole of anhydroglucose unit.
本発明のセルロース繊維の置換度は０．０１以上０．５以下、より好ましくは０．０１以上０．２５以下である。置換度が０．０１未満ではセルロース繊維の解繊が困難であり、０．５超ではセルロース繊維が水に溶解してしまうため増粘・分散安定効果を発現することが困難である。 The degree of substitution of the cellulose fiber of the present invention is 0.01 or more and 0.5 or less, more preferably 0.01 or more and 0.25 or less. If the degree of substitution is less than 0.01, it is difficult to defibrate the cellulose fiber, and if it exceeds 0.5, the cellulose fiber is dissolved in water, so that it is difficult to exhibit a thickening / dispersion stabilizing effect.
本発明のセルロース繊維はＩ型及び／又はＩＩ型の結晶構造を有する。結晶構造を有することは、例えば、広角Ｘ線回折像測定により得られる回折プロファイルにおいて、セルロースＩ型またはＩＩ型に典型的なＸ線回折パターン（Ｉ型：回折角２θ＝１４．８°、１６．８°、２２．６°、ＩＩ型：回折角２θ＝１２．１°、１９．８°、２２．０°）をもつことから確認できる。 The cellulose fiber of the present invention has a crystal structure of type I and / or type II. Having a crystal structure is, for example, an X-ray diffraction pattern typical of cellulose type I or type II (type I: diffraction angle 2θ = 14.8 °, 16 in a diffraction profile obtained by wide-angle X-ray diffraction image measurement. .8 °, 22.6 °, type II: diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °).
本発明のセルロース繊維は、アスペクト比が５０以上である。より好ましくは１００以上である。アスペクト比が５０未満の場合、ゲル状組成物がゲル状の性状を保持することが困難となる不具合が生じる。 The cellulose fiber of the present invention has an aspect ratio of 50 or more. More preferably, it is 100 or more. When the aspect ratio is less than 50, there is a problem that it is difficult for the gel-like composition to maintain the gel-like properties.
上記セルロースのアスペクト比は、例えば以下の方法で測定することが出来る。すなわ
ち、セルロースを親水化処理済みのカーボン膜被覆グリッド上にキャストした後、２％ウ
ラニルアセテートでネガティブ染色したＴＥＭ像（倍率：１００００倍）から、セルロー
スの短幅の方の数平均幅、および長幅の方の数平均幅を観察した。すなわち、各先に述べ
た方法に従い、短幅の方の数平均幅、および長幅の方の数平均幅を算出し、これらの値を
用いてアスペクト比を下記の式（１）に従い算出した。
The aspect ratio of the cellulose can be measured, for example, by the following method. That is, from a TEM image (magnification: 10000 times) negatively stained with 2% uranyl acetate after cellulose was cast on a hydrophilic membrane-coated carbon film-coated grid, the number average width and length of the short side of cellulose The number average width of the width was observed. That is, the number average width of the shorter width and the number average width of the longer width are calculated according to the methods described above, and the aspect ratio is calculated according to the following formula (1) using these values. .
本発明のセルロース原料は、晒又は未晒木材パルプ、精製リンター、酢酸菌等の微生物によって生産されるセルロース等の天然セルロースや、セルロースを銅アンモニア溶液、モルホリン誘導体等、何らかの溶媒に溶解し、改めて紡糸された再生セルロース、及び上記セルロース系素材の加水分解、アルカリ加水分解、酵素分解、爆砕処理、振動ボールミル処理等によって解重合処理した微細セルロース又は機械的に処理した微細セルロースが例示される。 The cellulose raw material of the present invention is a natural cellulose such as cellulose produced by microorganisms such as bleached or unbleached wood pulp, refined linter, and acetic acid bacteria, and cellulose is dissolved in some solvent such as a copper ammonia solution and a morpholine derivative. Examples include spun regenerated cellulose and fine cellulose that has been depolymerized by hydrolysis, alkali hydrolysis, enzymatic decomposition, explosion treatment, vibration ball mill treatment, or the like, or mechanically processed fine cellulose.
本発明のセルロース繊維は、アニオン変性したセルロースを高圧ホモジナイザー等によって解繊処理することで得ることができる。高圧ホモジナイザーとは、ポンプによって流体に加圧し、流路に設けた非常に繊細な間隙より噴出させる装置である。粒子間の衝突、圧力差による剪断力等の総合エネルギーによって乳化・分散・解繊・粉砕・超微細化を行うことができる。 The cellulose fiber of the present invention can be obtained by fibrillating an anion-modified cellulose with a high-pressure homogenizer or the like. A high-pressure homogenizer is a device that pressurizes a fluid with a pump and ejects it from a very delicate gap provided in a flow path. It is possible to emulsify, disperse, defibrate, grind, and make ultrafine particles by using total energy such as collision between particles and shear force due to pressure difference.
本発明のホモジナイザーによる処理条件としては、特に限定されるものではないが、圧力条件としては、３０ＭＰａ以上、好ましくは１００ＭＰａ以上、さらに好ましくは１４０ＭＰａ以上である。また、高圧ホモジナイザーでの解繊・分散処理に先立って、必要に応じて、高速せん断ミキサーなどの公知の混合、攪拌、乳化、分散装置を用いて、アニオン変性されたセルロースに予備処理を施すことも可能である。 The treatment conditions with the homogenizer of the present invention are not particularly limited, but the pressure conditions are 30 MPa or more, preferably 100 MPa or more, more preferably 140 MPa or more. In addition, prior to defibration / dispersion treatment with a high-pressure homogenizer, if necessary, pretreatment of anion-modified cellulose is performed using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. Is also possible.
本発明の水系塗料組成物は、上記セルロース繊維と共に水系樹脂が用いられる。本発明
の水系塗料組成物に使用する水系樹脂としては、何ら制約はなく、例えば、水溶性の樹脂、ディスパージョン、エマルション、ミクロゲル等の形態を有する樹脂が使用できる。さらに具体的に上記水系樹脂を例示すると、アクリル系樹脂、アルキド系樹脂、ポリエステル系樹脂、ポリウレタン樹脂、アクリルウレタン樹脂、ブロックイソシアネート含有化合物、フッ素樹脂、エポキシ樹脂、エポキシアクリレート樹脂、フェノール樹脂、メラミン樹脂、ビニル系樹脂、ポリアミド樹脂、セルロース系樹脂等が挙げられる。さらに、本発明の水系塗料組成物に使用する水系樹脂には、重合または架橋により樹脂を潜在的に形成しうる化合物、いわゆる、モノマーやオリゴマーも含む。本特許において、ブロックイソシアネート含有化合物とは、ブロックイソシアネート樹脂、ブロックイソシアネートプレポリマー、ブロックイソシアネート含有オリゴマー、ブロックポリイソシアネート化合物などを指す。なお、プレポリマーとはモノマーの重合または縮合反応を適当な所で止めた中間生成物を指し、ブロックイソシアネートはブロック化イソシアネート、ブロックドイソシアネートと同義語として取り扱う。
In the aqueous coating composition of the present invention, an aqueous resin is used together with the cellulose fibers. There is no restriction | limiting as an aqueous resin used for the aqueous coating composition of this invention, For example, resin which has forms, such as a water-soluble resin, a dispersion, an emulsion, a microgel, can be used. More specifically, the above water-based resins are exemplified by acrylic resins, alkyd resins, polyester resins, polyurethane resins, acrylic urethane resins, blocked isocyanate-containing compounds, fluorine resins, epoxy resins, epoxy acrylate resins, phenol resins, melamine resins. Vinyl resin, polyamide resin, cellulose resin and the like. Furthermore, the water-based resin used in the water-based coating composition of the present invention includes compounds that can potentially form a resin by polymerization or crosslinking, so-called monomers and oligomers. In this patent, the blocked isocyanate-containing compound refers to a blocked isocyanate resin, a blocked isocyanate prepolymer, a blocked isocyanate-containing oligomer, a blocked polyisocyanate compound, and the like. The prepolymer refers to an intermediate product obtained by stopping the polymerization or condensation reaction of the monomer at an appropriate place, and the blocked isocyanate is treated as a synonym for the blocked isocyanate and the blocked isocyanate.
本発明の水系塗料組成物は、上記セルロース繊維及び水系樹脂と共に着色剤が用いられ
る。
In the water-based coating composition of the present invention, a colorant is used together with the cellulose fiber and the water-based resin.
本発明の水系塗料組成物に使用する着色剤としては、何ら制約はなく、例えば、有機および無機の顔料、体質顔料、蛍光顔料、染料、蛍光染料等が挙げられる。さらに具体的に例示すると、亜鉛華、亜酸化銅、一酸化鉛、ウォッチングレッド、マイカ、酸化チタン、オイルファーネスブラック、黄鉛、黄色酸化鉄、オキシサルファイド蛍光体、カオリンクレー、滑石、石筆石、石鹸石、カドミウムイエロー、カドミウムレッド、燐酸カルシウム、アルミナ、群青、蛍光顔料、軽質炭酸カルシウム、合成マイカ、黒鉛、黒色酸化鉄、コバルト青、コバルト緑、コバルト紫、胡粉、紺青、サーマルブラック、酸化クロム、酸化チタン（アタナース）、酸化チタン（ルチル）、ジスアゾイエロー、重質炭酸カルシウム、焼成クレー、赤色酸化鉄、カーボンブラック、茶色酸化鉄、チャンネルブラック、超微粒子状酸化亜鉛、超微粒子状酸化チタン、硫酸バリウム、鉄黒、天然黒鉛粉末、天然土状黒鉛、銅フタロシアニンブルー、銅フタロシアニングリーン、パーマネントレッド、バナデート蛍光体、表面処理硫酸バリウム、微粒子硫酸バリウム、微粒子水酸化アルミニウム、ファストイエロー１０Ｇ、ベンガラ、ホワイトカーボン、モリブデンレッド等が挙げられる。これら着色剤は表面処理されたものを使用してもよく、また、あらかじめ樹脂または媒質中に分散処理されたものを使用してもよい。 There is no restriction | limiting as a coloring agent used for the water-based coating composition of this invention, For example, an organic and inorganic pigment, extender pigment, fluorescent pigment, dye, fluorescent dye etc. are mentioned. More specifically, zinc white, cuprous oxide, lead monoxide, watching red, mica, titanium oxide, oil furnace black, chrome lead, yellow iron oxide, oxysulfide phosphor, kaolin clay, talc, calcite, Soapstone, cadmium yellow, cadmium red, calcium phosphate, alumina, ultramarine, fluorescent pigment, light calcium carbonate, synthetic mica, graphite, black iron oxide, cobalt blue, cobalt green, cobalt purple, turquoise, bituminous, thermal black, chromium oxide , Titanium oxide (Atanus), titanium oxide (rutile), disazo yellow, heavy calcium carbonate, calcined clay, red iron oxide, carbon black, brown iron oxide, channel black, ultrafine zinc oxide, ultrafine titanium oxide, Barium sulfate, iron black, natural graphite powder, natural earth graphite, copper lid Cyanine blue, copper phthalocyanine green, permanent red, vanadate phosphor, surface treatment barium sulfate, particulate barium sulfate, aluminum particles hydroxide, Fast Yellow 10G, red iron oxide, white carbon, molybdenum red, and the like. These colorants may be surface-treated, or those previously dispersed in a resin or medium may be used.
本発明の水系塗料組成物には、上記セルロース繊維、水系樹脂及び着色剤に加えて、水
が用いられる。
In the water-based coating composition of the present invention, water is used in addition to the cellulose fiber, the water-based resin and the colorant.
さらに、本発明の水系塗料組成物には必要に応じて、本発明の効果を妨げない範囲で任意成分を含むことができる。 Furthermore, the water-based coating composition of the present invention can contain an optional component as long as it does not interfere with the effects of the present invention.
上記任意成分としては、ラメ剤、パール剤、防腐剤、香料、可塑剤、消泡剤、充填剤、
酸化防止剤、紫外線吸収剤、硬化剤、触媒、溶剤、界面活性剤、水溶性高分子、難燃剤、
帯電防止剤、熱安定剤、ｐH調整剤、凍結防止剤、湿潤剤、顔料分散剤、乳化剤、皮張り防止剤、レベリング剤、乾燥促進剤等の添加剤が挙げられる。
As the above optional components, lame, pearl, preservative, fragrance, plasticizer, antifoaming agent, filler,
Antioxidants, UV absorbers, curing agents, catalysts, solvents, surfactants, water-soluble polymers, flame retardants,
Examples thereof include additives such as antistatic agents, heat stabilizers, pH adjusting agents, antifreezing agents, wetting agents, pigment dispersants, emulsifiers, antiskinning agents, leveling agents, and drying accelerators.
本発明の水系塗料組成物は、上記セルロース繊維、水系樹脂、着色剤、水、および、必要であればその他の任意の添加物を混合・分散することにより製造される。その混合方法と混合順序に制約はない。 The water-based coating composition of the present invention is produced by mixing and dispersing the cellulose fiber, water-based resin, colorant, water, and, if necessary, any other additive. There is no restriction on the mixing method and mixing order.
本発明の水系塗料組成物の製造方法は具体的には下記の通りである。すなわち、上記セ
ルロース繊維を、あらかじめ水中で混合・分散処理して、平均繊維径を２ｎｍ以上５００ｎｍ以下にした水分散体を調製しておき、本発明の水系塗料組成物に配合してもよく、また、本発明の水系塗料組成物を製造する際に実施される、混合・分散処理と同時に、上記セルロース繊維の分散を行い、平均繊維径を２ｎｍ以上５００ｎｍ以下にした上記セルロース繊維としてもよい。本発明の水系塗料組成物を製造する際の合理性からすれば、後者の方法が好ましい。
The method for producing the water-based coating composition of the present invention is specifically as follows. That is, the cellulose fiber is previously mixed and dispersed in water to prepare an aqueous dispersion having an average fiber diameter of 2 nm or more and 500 nm or less, and may be blended in the aqueous coating composition of the present invention. Moreover, it is good also as the said cellulose fiber which disperse | distributed the said cellulose fiber simultaneously with the mixing and dispersion | distribution process implemented when manufacturing the water-based coating composition of this invention, and made the average fiber diameter 2 nm or more and 500 nm or less. The latter method is preferable from the viewpoint of rationality in producing the water-based coating composition of the present invention.
上記混合・分散を行う装置としては、プロペラ型、パドル型、アンカー型等の混合機、ホモミキサー、ホモディスパー、ホモジナイザー、高圧ホモジナイザー、超高圧ホモジナイザー、超音波ホモジナイザー、振動ミル、ボールミル、遊星ボールミル、サンドミル、真空乳化装置、ペイントシェーカー等が挙げられる。 The mixing / dispersing apparatus includes a propeller type, paddle type, anchor type mixer, homomixer, homodisper, homogenizer, high pressure homogenizer, ultrahigh pressure homogenizer, ultrasonic homogenizer, vibration mill, ball mill, planetary ball mill, A sand mill, a vacuum emulsifier, a paint shaker, etc. are mentioned.
本発明の水系塗料組成物における、上記セルロース繊維の配合量は、通常０．０１質量
％以上３質量％以下、好ましくは０．０５質量％以上２質量％以下の範囲内である。０．０１質量％以下では水系塗料組成物への粘性付与が困難となり、増粘安定効果が不十分となるので好ましくない。３質量％以上では水系塗料組成物の粘度が高過ぎて、塗料製造時のハンドリングが難しく、塗料使用時の塗工性、塗膜性が悪化するので好ましくない。
The blending amount of the cellulose fiber in the water-based coating composition of the present invention is usually 0.01% by mass to 3% by mass, preferably 0.05% by mass to 2% by mass. If it is 0.01% by mass or less, it is difficult to impart viscosity to the water-based coating composition, and the thickening and stabilizing effect becomes insufficient, which is not preferable. If it is 3% by mass or more, the viscosity of the water-based coating composition is too high, it is difficult to handle at the time of coating production, and the coating properties and coating properties at the time of using the coating are deteriorated.
本発明の水系塗料組成物の粘度は、上記特定のセルロース繊維の配合量により調整することができる。すなわち、上記特定のセルロース繊維の配合量を増やすと粘度は増加する傾向にあり、上記特定のセルロース繊維の配合量を減らすと粘度は低下する傾向にある。 The viscosity of the water-based coating composition of the present invention can be adjusted by the blending amount of the specific cellulose fiber. That is, when the amount of the specific cellulose fiber is increased, the viscosity tends to increase, and when the amount of the specific cellulose fiber is decreased, the viscosity tends to decrease.
上記特定のセルロース繊維の配合量により、本発明の水系塗料組成物の粘度は１００ｍＰａ・ｓから１０００００ｍＰａ・ｓの範囲に調整することが可能であり、流動状態の水系塗料組成物から、必要に応じて、ペースト状またはゲル状の水系塗料組成物とすることができる。 The viscosity of the aqueous coating composition of the present invention can be adjusted in the range of 100 mPa · s to 100000 mPa · s depending on the blending amount of the specific cellulose fiber. Thus, a water-based paint composition in the form of a paste or gel can be obtained.
また、本発明の水系塗料組成物の粘度は、上記特定のセルロース繊維の配合量以外に、水系樹脂成分や着色剤の種類と配合量、および任意成分の種類と配合量の影響を受けるので、個別の水系塗料組成物ごとに粘度の調整を行うことが好ましい。 In addition, the viscosity of the water-based coating composition of the present invention is affected by the types and amounts of water-based resin components and colorants, as well as the types and amounts of optional components, in addition to the specific cellulose fiber content. It is preferable to adjust the viscosity for each water-based coating composition.
本発明の水系塗料組成物における上記水系樹脂の配合量は、樹脂固形分として、通常、０質量％以上８０質量％以下、好ましくは０．１質量％以上６０質量％以下の範囲である。上記配合量が樹脂固形分８０質量％超では水系塗料組成物の流動性が保たれず、ハンドリングが難しくなるため好ましくない。 The blending amount of the water-based resin in the water-based coating composition of the present invention is usually in the range of 0 to 80% by mass, preferably 0.1 to 60% by mass as the resin solid content. If the blending amount exceeds 80% by mass of the resin solid content, the fluidity of the water-based coating composition is not maintained, and handling becomes difficult.
本発明の水系塗料組成物における上記着色剤の配合量は、通常、０質量％以上８０質量％、以下好ましくは０質量％以上６０質量％以下の範囲である。本発明の水系塗料組成物がクリヤー塗料の場合には配合量は０質量％となる。８０質量％以上では水系塗料組成物の流動性が保たれず、ハンドリングが難しくなるため好ましくない。 The blending amount of the colorant in the water-based coating composition of the present invention is usually in the range of 0 to 80% by mass, preferably 0 to 60% by mass. When the water-based paint composition of the present invention is a clear paint, the blending amount is 0% by mass. If it is 80% by mass or more, the fluidity of the water-based coating composition is not maintained, and handling becomes difficult.
本発明の水系塗料組成物の塗工方法にはなんら制約はなく、例えば刷毛、バーコーター、ロールコーター、スプレー、浸漬、電着、焼付、筆記、印刷、インクジェット印刷等により塗工できる。
本発明の水系塗料組成物に配合される上記特定のセルロース繊維は、チキソトロピーイ
ンデックスが大きいため、水系塗料組成物の粘度が高い場合であっても、スプレー塗工が
可能である。
There is no restriction | limiting in the coating method of the water-system coating composition of this invention, For example, it can apply by brush, a bar coater, a roll coater, spray, immersion, electrodeposition, baking, writing, printing, inkjet printing etc.
Since the specific cellulose fiber blended in the aqueous coating composition of the present invention has a large thixotropic index, spray coating is possible even when the aqueous coating composition has a high viscosity.
本発明の水系塗料組成物を塗工する基材、としては、何ら制約はなく、例えば、紙、木
材、樹脂、金属、ガラス、セメント、アスファルト、皮革等が挙げられる。
本発明の水系塗料組成物の用途としては、何ら制約はなく、例えば、建築、建材、自動車、船舶、鉄道、航空機、機械、構造物、自動車補修、家電、繊維、皮革、文房具、木工、家具、雑貨、鋼板、缶、電子基板、電子部品、印刷等の用途に水系塗料または水系インクとして利用することができる。
There is no restriction | limiting as a base material which applies the water-system coating composition of this invention, For example, paper, wood, resin, a metal, glass, cement, asphalt, leather etc. are mentioned.
There are no restrictions on the use of the water-based paint composition of the present invention, for example, construction, building materials, automobiles, ships, railways, aircraft, machines, structures, automobile repairs, home appliances, textiles, leather, stationery, woodworking, furniture. It can be used as a water-based paint or water-based ink for applications such as miscellaneous goods, steel plates, cans, electronic substrates, electronic parts, and printing.
つぎに、実施例について比較例と併せて説明する。ただし、本発明はこれら実施例に限定されるものではない。 Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.
＜セルロース繊維各項目の測定方法＞
[グルコース単位当たりの置換度の測定方法]
セルロース繊維を０．６質量％スラリーに調製し、０．１Ｍ塩酸水溶液を加えてｐＨ２．４とした後、０．０５Ｎの水酸化ナトリウム水溶液を滴下してｐＨが１１になるまで電気伝導度を測定し、電気伝導度の変化が緩やかな弱酸の中和段階において消費された水酸化ナトリウム量からカルボキシル基量を測定し、下式を用いて算出した。ここで言う置換度とは、無水グルコース単位１モル当たりの置換基のモル数の平均値を表している。
<Measurement method of each item of cellulose fiber>
[Measurement method of substitution degree per glucose unit]
Cellulose fiber is prepared in a slurry of 0.6% by mass, 0.1M hydrochloric acid aqueous solution is added to adjust the pH to 2.4, and 0.05N sodium hydroxide aqueous solution is added dropwise until the pH reaches 11. The amount of carboxyl groups was measured from the amount of sodium hydroxide consumed in the neutralization step of a weak acid with a gradual change in electrical conductivity, and calculated using the following formula. The degree of substitution referred to here represents the average value of the number of moles of substituents per mole of anhydroglucose unit.
セルロース繊維に水を加えて２質量％のスラリーとして、ディスパー型ミキサーを用いて回転数８，０００ｒｐｍで１０分間微細化処理を行った。各セルロース繊維の最大繊維径および数平均繊維径を、透過型電子顕微鏡（ＴＥＭ）（日本電子社製、ＪＥＭ−１４００）を用いて観察した。すなわち、各セルロース繊維を親水化処理済みのカーボン膜被覆グリッド上にキャストした後、２％ウラニルアセテートでネガティブ染色したＴＥＭ像（倍率：１００００倍）から、先に述べた方法に従い、数平均繊維径を算出した。
Water was added to the cellulose fiber to make a slurry of 2 mass%, and a finer treatment was performed for 10 minutes at a rotation speed of 8,000 rpm using a disper type mixer. The maximum fiber diameter and the number average fiber diameter of each cellulose fiber were observed using a transmission electron microscope (TEM) (JEM-1400, manufactured by JEOL Ltd.). That is, after each cellulose fiber was cast on a hydrophilized carbon film-coated grid and negatively stained with 2% uranyl acetate, the number average fiber diameter was determined according to the method described above. Was calculated.
＜結晶構造の確認方法＞
Ｘ線回折装置（リガク社製、ＲＩＮＴ−Ｕｌｔｉｍａ３）を用いて広角Ｘ線回折像を測定し、各セルロース繊維の回折プロファイルにセルロースＩ型またはＩＩ型に典型的なＸ線回折パターン（Ｉ型：回折角２θ＝１４．８°、１６．８°、２２．６°、ＩＩ型：回折角２θ＝１２．１°、１９．８°、２２．０°）がみられる場合は結晶構造を有すると判断した。
<Confirmation method of crystal structure>
A wide-angle X-ray diffraction image was measured using an X-ray diffractometer (RINT-Ultima 3 manufactured by Rigaku Corporation), and an X-ray diffraction pattern typical of cellulose type I or type II (type I: (Diffraction angle 2θ = 14.8 °, 16.8 °, 22.6 °, type II: diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °) I decided.
＜アスペクト比の測定方法＞
セルロースを親水化処理済みのカーボン膜被覆グリッド上にキャストした後、２％ウラニルアセテートでネガティブ染色したＴＥＭ像（倍率：１００００倍）から、セルロースの短幅の方の数平均幅、長幅の方の数平均幅を観察した。すなわち、各先に述べた方法に従い、短幅の方の数平均幅、および長幅の方の数平均幅を算出し、これらの値を用いてアスペクト比を前述の式（１）に従い算出した。
<Aspect ratio measurement method>
From the TEM image (magnification: 10000 times) that was negatively stained with 2% uranyl acetate after the cellulose was cast on a hydrophilic membrane-coated carbon film grid, the number average width and the long width of the short width of cellulose The number average width of was observed. That is, the number average width of the shorter width and the number average width of the longer width are calculated according to the methods described above, and the aspect ratio is calculated according to the above-described formula (1) using these values. .
〔製造例１〕
撹拌機に、パルプ（ＬＢＫＰ、日本製紙（株）製）を乾燥質量で２００ｇ、水酸化ナトリウムを乾燥質量で１８ｇ加え、パルプ固形分濃度が１５％になるように水を加えた。その後、３０℃で３０分攪拌した後に７０℃まで昇温し、モノクロロ酢酸ナトリウムを２３ｇ（有効成分換算）添加した。１時間反応した後に、反応物を取り出して中和、洗浄して、グルコース単位当たりの置換度０．０１のアニオン変性されたセルロースを得た。その後、アニオン変性したパルプに水を添加して固形分濃度５％とし、高圧ホモジナイザーにより２０℃、１４０ＭＰａの圧力で５回処理し、数平均繊維径７４ｎｍ、アスペクト比６７で、結晶構造を有するセルロース繊維１の分散液を得た。
[Production Example 1]
To the stirrer, 200 g of pulp (LBKP, Nippon Paper Industries Co., Ltd.) in dry mass and 18 g of sodium hydroxide in dry mass were added, and water was added so that the pulp solid content concentration was 15%. Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 23 g (in terms of active ingredient) of sodium monochloroacetate was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a substitution degree of 0.01 per glucose unit. Thereafter, water was added to the anion-modified pulp to a solid content concentration of 5%, and it was treated 5 times with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa, and the number-average fiber diameter was 74 nm, the aspect ratio was 67, and the cellulose having a crystal structure A dispersion of fiber 1 was obtained.
〔製造例２〕
水酸化ナトリウムを１７６ｇ、モノクロロ酢酸ナトリウムを２３４ｇ（有効成分換算）に変更した以外、製造例１と同様にしてセルロース繊維２の分散液を得た。なお、得られたセルロース繊維のグルコース単位当たりの置換度は０．１０であり、数平均繊維径は１０ｎｍ、アスペクト比１４０で、結晶構造を有していた。
[Production Example 2]
A dispersion of cellulose fiber 2 was obtained in the same manner as in Production Example 1 except that 176 g of sodium hydroxide and 234 g of sodium monochloroacetate (active ingredient conversion) were changed. In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.10, the number average fiber diameter was 10 nm, the aspect ratio was 140, and it had a crystal structure.
〔製造例３〕
水酸化ナトリウムを３０８ｇ、モノクロロ酢酸ナトリウムを４１０ｇ（有効成分換算）に変更した以外、製造例１と同様にしてセルロース繊維３の分散液を得た。なお、得られたセルロース繊維のグルコース単位当たりの置換度は０．２５であり、数平均繊維径は６ｎｍ、アスペクト比１６０で、結晶構造を有していた。
[Production Example 3]
A dispersion of cellulose fiber 3 was obtained in the same manner as in Production Example 1, except that sodium hydroxide was changed to 308 g and sodium monochloroacetate was changed to 410 g (in terms of active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.25, the number average fiber diameter was 6 nm, the aspect ratio was 160, and it had a crystal structure.
〔製造例４〕
水酸化ナトリウムを９ｇ、モノクロロ酢酸ナトリウムを１２ｇ（有効成分換算）に変更した以外、製造例１と同様にしてセルロース繊維４の分散液を得た。なお、得られたセルロース繊維のグルコース単位当たりの置換度は０．００５であり、数平均繊維径は６２０ｎｍ、アスペクト比１８で、結晶構造を有していた。
[Production Example 4]
A dispersion of cellulose fiber 4 was obtained in the same manner as in Production Example 1, except that the sodium hydroxide was changed to 9 g and the sodium monochloroacetate was changed to 12 g (converted to the active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.005, the number average fiber diameter was 620 nm, the aspect ratio was 18, and it had a crystal structure.
〔製造例５〕
水酸化ナトリウムを４７６ｇ、モノクロロ酢酸ナトリウムを６３２ｇ（有効成分換算）に変更した以外、製造例１と同様にしてセルロース繊維５の分散液を得た。なお、得られたセルロースのグルコース単位当たりの置換度は０．６であり、数平均繊維径は測定できず、結晶構造はみられなかった。
[Production Example 5]
A dispersion of cellulose fiber 5 was obtained in the same manner as in Production Example 1, except that sodium hydroxide was changed to 476 g and sodium monochloroacetate was changed to 632 g (in terms of active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose was 0.6, the number average fiber diameter could not be measured, and no crystal structure was observed.
〔製造例６〕
水酸化ナトリウムを３０８ｇ、モノクロロ酢酸ナトリウムを４１０ｇ（有効成分換算）、高圧ホモジナイザーによる処理を２０回に変更した以外、製造例１と同様にしてセルロース繊維６の分散液を得た。なお、得られたセルロース繊維のグルコース単位当たりの置換度は０．２５であり、数平均繊維径は測定できず、結晶構造はみられなかった。
[Production Example 6]
A dispersion of cellulose fiber 6 was obtained in the same manner as in Production Example 1, except that 308 g of sodium hydroxide, 410 g of sodium monochloroacetate (converted to active ingredients), and the treatment with the high-pressure homogenizer were changed to 20 times. In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.25, the number average fiber diameter could not be measured, and no crystal structure was observed.
〔製造例７〕
撹拌機に、パルプ（ＬＢＫＰ、日本製紙（株）製）を乾燥質量で２００ｇ、水酸化ナトリウムを乾燥質量で３０８ｇ加え、パルプ固形分濃度が１５％になるように水を加えた。その後、７０℃で９時間攪拌した後に、モノクロロ酢酸ナトリウムを４１０ｇ（有効成分換算）添加した。１時間反応した後に、反応物を取り出して中和、洗浄して、グルコース単位当たりの置換度０．２８のアニオン変性されたセルロースを得た。その後、アニオン変性したパルプに水を添加して固形分濃度５％とし、高圧ホモジナイザーにより２０℃、１４０ＭＰａの圧力で５回処理し、セルロース繊維７の分散液を得た。数平均繊維径は測定できず、結晶構造はみられなかった。
[Production Example 7]
To a stirrer, 200 g of pulp (LBKP, manufactured by Nippon Paper Industries Co., Ltd.) in dry mass and 308 g of sodium hydroxide in dry mass were added, and water was added so that the pulp solid content concentration was 15%. Then, after stirring for 9 hours at 70 ° C., 410 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a substitution degree of 0.28 per glucose unit. Thereafter, water was added to the anion-modified pulp to a solid content concentration of 5%, and it was treated 5 times with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa to obtain a dispersion of cellulose fibers 7. The number average fiber diameter could not be measured, and no crystal structure was observed.
〔セルロース微粒子〕
繊維表面が酸化されていない、セルロース微粒子分散体を調製した。すなわち、セルロース（木材パルプから製造したサルファイトパルプ）を、固形分濃度１質量％となるように水に分散させ、石臼型グラインダーで１５回処理を行い、繊維表面が酸化されていないセルロース微粒子分散体を調製した。下記の方法でセルロース繊維の数平均繊維径を測定したところ、４μｍであった。
[Cellulose fine particles]
A cellulose fine particle dispersion in which the fiber surface was not oxidized was prepared. That is, cellulose (sulfite pulp produced from wood pulp) is dispersed in water so as to have a solid content concentration of 1% by mass, treated with a stone mill grinder 15 times, and cellulose fine particles whose fiber surface is not oxidized are dispersed. The body was prepared. It was 4 micrometers when the number average fiber diameter of the cellulose fiber was measured by the following method.
＜水性塗料組成物の評価＞
〔実施例１〕
着色剤である酸化チタン１５質量部並びに炭酸カルシウム７質量部、界面活性剤であるポリオキシエチレンポリオキシプロピレンブロック重合体（製品名：エパン７１０、第一工業製薬株式会社製）０．６質量部、及び水（顔料分散用）２０質量部を計量し、ビーズミルで分散処理をして、顔料分散液を調製した。得られた顔料分散液、セルロース繊維１を固形分換算値で０．２質量部、及び水系ウレタン樹脂エマルションを固形分換算値で１８質量部を計量し水を加えて１００質量部とした。次に、ホモミキサーを用いて、１２０００ｒｐｍで１５分間混合して、水系塗料組成物を得た。
<Evaluation of aqueous coating composition>
[Example 1]
15 parts by mass of titanium oxide as a colorant and 7 parts by mass of calcium carbonate, 0.6 parts by mass of polyoxyethylene polyoxypropylene block polymer as a surfactant (product name: Epan 710, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) And 20 parts by mass of water (for pigment dispersion) were weighed and dispersed with a bead mill to prepare a pigment dispersion. 0.2 parts by mass of the obtained pigment dispersion and cellulose fiber 1 in terms of solid content, and 18 parts by mass of the water-based urethane resin emulsion in terms of solid content were weighed and water was added to make 100 parts by mass. Next, it mixed for 15 minutes at 12000 rpm using the homomixer, and obtained the water-system coating composition.
〔実施例２、３、比較例１〜５〕
セルロース繊維１をセルロース繊維２ないし５、及びセルロース粒子に変更する以外は、実施例１に準じて水系塗料組成物を得た。
[Examples 2 and 3, Comparative Examples 1 to 5]
A water-based coating composition was obtained according to Example 1 except that the cellulose fiber 1 was changed to cellulose fibers 2 to 5 and cellulose particles.
このようにして得られた各水系塗料組成物を用い、下記の基準に従って、各特性の評価
を行った。
[分散性]
水系塗料組成物を目視観察し、顔料の分散状態を下記の判定基準に従い判定した。
○：顔料が均一に分散している。
△：一部に分離がみられる。
×：完全に分離している。
Each characteristic was evaluated according to the following reference | standard using each water-based coating composition obtained in this way.
[Dispersibility]
The water-based paint composition was visually observed, and the dispersion state of the pigment was determined according to the following criteria.
○: The pigment is uniformly dispersed.
Δ: Partial separation is observed.
X: Completely separated.
[保存性]
水系塗料組成物を、共栓付メスシリンダーに移し、４０℃で１週間放置した後、下記の判定基準に従い組成物の分離状態を目視で判定した。
○：顔料が均一に分散している。
△：一部に分離がみられる。
×：完全に分離している。
[Preservation]
The aqueous coating composition was transferred to a measuring cylinder with a stopper and allowed to stand at 40 ° C. for 1 week, and then the separation state of the composition was visually determined according to the following criteria.
○: The pigment is uniformly dispersed.
Δ: Partial separation is observed.
X: Completely separated.
[タレ性]
得られた水系塗料組成物を、バーコーター（Ｋ−ハンドコーター、ＲＫ ＰｒＩｎｔ−Ｃｏａｔ Ｉｎｓｔｒｕｍｅｎｔ社製）を用いて、垂直に保持した亜鉛メッキ鋼板に塗工し、塗料のタレ状態を下記の判定基準に従い目視で判定した。
○：塗工後１０分以上タレがみられない。
△：塗工後１０分以内にタレがみられる。
×：塗工直後からタレがみられる。
[Sag]
The obtained water-based paint composition was applied to a galvanized steel sheet held vertically using a bar coater (K-hand coater, manufactured by RK PrInt-Coat Instrument), and the sagging state of the paint was determined according to the following criteria. And judged visually.
○: Sagging is not observed for 10 minutes or more after coating.
Δ: Sagging is observed within 10 minutes after coating.
X: Sagging is observed immediately after coating.
[耐水性]
水系塗料組成物を、バーコーター（Ｋ−ハンドコーター、ＲＫ ＰｒＩｎｔ−Ｃｏａｔ Ｉｎｓｔｒｕｍｅｎｔ社製）を用いて、亜鉛メッキ鋼板に塗工した後、４０℃で２４時間乾燥し、さらに、２５℃の水中に１０日間浸漬した後、塗膜の状態を下記の判定基準に従い目視で判定した。
○：塗膜の剥がれや膨れがみとめられない。
△：一部に塗膜の剥がれや膨れがみとめられる。
×：全体に塗膜の剥がれや膨れがみとめられる。
[water resistant]
The water-based coating composition was applied to a galvanized steel sheet using a bar coater (K-hand coater, manufactured by RK PrInt-Coat Instrument), dried at 40 ° C. for 24 hours, and further immersed in 25 ° C. water. After immersion for 10 days, the state of the coating film was visually determined according to the following criteria.
○: No peeling or swelling of the coating film is observed.
Δ: Peeling or swelling of the coating film is partially observed.
X: Peeling and swelling of the coating film are observed throughout.
本発明の活用例として、建築、建材、自動車、船舶、鉄道、航空機、機械、構造物、自
動車補修、家電、繊維、皮革、文房具、木工、家具、雑貨、鋼板、缶、電子基板、電子部
品、印刷、等の用途に水系塗料または水系インクとして利用することができる。
Examples of use of the present invention include construction, building materials, automobiles, ships, railways, aircraft, machinery, structures, automobile repairs, home appliances, textiles, leather, stationery, woodwork, furniture, sundries, steel plates, cans, electronic boards, electronic components It can be used as a water-based paint or water-based ink for applications such as printing.
Claims (3)
ン樹脂、アクリルウレタン樹脂、ブロックイソシアネート含有化合物、フッ素樹脂、エポキシ樹脂、エポキシアクリレート樹脂、フェノール樹脂、メラミン樹脂、ビニル系樹脂、ポリアミド樹脂及びセルロース系樹脂から選択される１種又は２種以上であることを特徴とする請求項１に記載の水系塗料組成物。 The water-based resin is an acrylic resin, alkyd resin, polyester resin, polyurethane resin, acrylic urethane resin, block isocyanate-containing compound, fluororesin, epoxy resin, epoxy acrylate resin, phenol resin, melamine resin, vinyl resin, polyamide The water-based coating composition according to claim 1, wherein the water-based coating composition is one or more selected from a resin and a cellulose-based resin.
The content of the cellulose fiber is 0.01% by mass to 3% by mass, the content of the aqueous resin is 0% by mass to 80% by mass as the resin solid part, and the content of the colorant is 0% by mass to 80%. The water-based coating composition according to claim 1 or 2, wherein the water-based coating composition is not more than mass%.
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