JP4673010B2 - Curable water-based resin composition - Google Patents
Curable water-based resin composition Download PDFInfo
- Publication number
- JP4673010B2 JP4673010B2 JP2004189214A JP2004189214A JP4673010B2 JP 4673010 B2 JP4673010 B2 JP 4673010B2 JP 2004189214 A JP2004189214 A JP 2004189214A JP 2004189214 A JP2004189214 A JP 2004189214A JP 4673010 B2 JP4673010 B2 JP 4673010B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerizable unsaturated
- monomer
- unsaturated monomer
- weight
- meth
- 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.)
- Expired - Fee Related
Links
- 239000011342 resin composition Substances 0.000 title claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 47
- 239000000178 monomer Substances 0.000 claims description 262
- 229920005989 resin Polymers 0.000 claims description 81
- 239000011347 resin Substances 0.000 claims description 81
- 150000004665 fatty acids Chemical class 0.000 claims description 64
- 238000000576 coating method Methods 0.000 claims description 63
- 239000006185 dispersion Substances 0.000 claims description 57
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 53
- 239000000194 fatty acid Substances 0.000 claims description 53
- 229930195729 fatty acid Natural products 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 33
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 21
- 239000008199 coating composition Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000002429 hydrazines Chemical class 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 239000012736 aqueous medium Substances 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 229930195734 saturated hydrocarbon Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Chemical group 0.000 claims description 5
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 95
- -1 3,4-epoxycyclohexylmethyl Chemical group 0.000 description 64
- 239000011248 coating agent Substances 0.000 description 61
- 238000001035 drying Methods 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 18
- 239000000049 pigment Substances 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 235000013372 meat Nutrition 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 229920000180 alkyd Polymers 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 5
- 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 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229920002253 Tannate Polymers 0.000 description 4
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000012874 anionic emulsifier Substances 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 229960002887 deanol Drugs 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 3
- 239000002320 enamel (paints) Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ZKECVHXIVHRIIA-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-1-yl)prop-2-enamide Chemical compound CC1(C)CCCC(C)(C)N1NC(=O)C=C ZKECVHXIVHRIIA-UHFFFAOYSA-N 0.000 description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl 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])[H] 0.000 description 3
- 235000002949 phytic acid Nutrition 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- 125000002889 tridecyl 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])[H] 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 2
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 2
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 2
- USAYMJGCALIGIG-UHFFFAOYSA-N 2,3-dichlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=C(Cl)C(=O)C=CC1=O USAYMJGCALIGIG-UHFFFAOYSA-N 0.000 description 2
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 2
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 2
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N 3-phenylprop-2-enal Chemical compound O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 2
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 235000019485 Safflower oil Nutrition 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002832 nitroso derivatives Chemical class 0.000 description 2
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- LWNSNYBMYBWJDN-UHFFFAOYSA-N octyl 3-sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)CCS LWNSNYBMYBWJDN-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- 229940080818 propionamide Drugs 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 235000005713 safflower oil Nutrition 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- AJOJTMNIQSTBAP-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-3-yl) prop-2-enoate Chemical compound CN1C(C)(C)CCC(OC(=O)C=C)C1(C)C AJOJTMNIQSTBAP-UHFFFAOYSA-N 0.000 description 1
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- GIIUJJXXMYYQQD-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)C=C GIIUJJXXMYYQQD-UHFFFAOYSA-N 0.000 description 1
- XMCLXVNPGNYTRE-VOTSOKGWSA-N (2,2,6,6-tetramethylpiperidin-4-yl) (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC1CC(C)(C)NC(C)(C)C1 XMCLXVNPGNYTRE-VOTSOKGWSA-N 0.000 description 1
- FLYXGBNUYGAFAC-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(2-hydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1O FLYXGBNUYGAFAC-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-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
- SNVRDQORMVVQBI-OWOJBTEDSA-N (e)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C\C(=O)NN SNVRDQORMVVQBI-OWOJBTEDSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-N 0.000 description 1
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- AXWKRUFUAGYTHB-UHFFFAOYSA-N 2-butylbenzenethiol Chemical compound CCCCC1=CC=CC=C1S AXWKRUFUAGYTHB-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- TZMACLAARXHRRZ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarbohydrazide Chemical compound NNC(=O)CC(O)(C(=O)NN)CC(=O)NN TZMACLAARXHRRZ-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- NEWFQHAOPHWBPR-UHFFFAOYSA-N 2-methylidenebutanedihydrazide Chemical compound NNC(=O)CC(=C)C(=O)NN NEWFQHAOPHWBPR-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZZURXLMHTYYCST-UHFFFAOYSA-N 2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS ZZURXLMHTYYCST-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- MQAHWZHKYCRCBC-UHFFFAOYSA-N 4-[(3-carboxy-1-cyanopropyl)diazenyl]-4-cyanobutanoic acid Chemical compound OC(=O)CCC(C#N)N=NC(C#N)CCC(O)=O MQAHWZHKYCRCBC-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FJNCXZZQNBKEJT-UHFFFAOYSA-N 8beta-hydroxymarrubiin Natural products O1C(=O)C2(C)CCCC3(C)C2C1CC(C)(O)C3(O)CCC=1C=COC=1 FJNCXZZQNBKEJT-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000008753 Papaver somniferum Nutrition 0.000 description 1
- 240000001090 Papaver somniferum Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000263 Rubber seed oil Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 235000019498 Walnut oil Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NHVINCKHPNHBJD-FIFLTTCUSA-N [1-[(e)-but-2-enoyl]-2,2,6,6-tetramethylpiperidin-4-yl] (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC1CC(C)(C)N(C(=O)\C=C\C)C(C)(C)C1 NHVINCKHPNHBJD-FIFLTTCUSA-N 0.000 description 1
- UBNGHBGXMXWFOS-UHFFFAOYSA-N [2-hydroxy-3-[3-hydroxy-4-(2-hydroxybenzoyl)phenoxy]propyl] 2-methylprop-2-enoate Chemical compound OC1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1O UBNGHBGXMXWFOS-UHFFFAOYSA-N 0.000 description 1
- QGZDXPBGRTUIQP-UHFFFAOYSA-N [2-hydroxy-3-[3-hydroxy-4-(2-hydroxybenzoyl)phenoxy]propyl] prop-2-enoate Chemical compound OC1=CC(OCC(COC(=O)C=C)O)=CC=C1C(=O)C1=CC=CC=C1O QGZDXPBGRTUIQP-UHFFFAOYSA-N 0.000 description 1
- LUWALSGLYLSCKN-UHFFFAOYSA-N [3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxypropyl] prop-2-enoate Chemical compound OC1=CC(OCC(COC(=O)C=C)O)=CC=C1C(=O)C1=CC=CC=C1 LUWALSGLYLSCKN-UHFFFAOYSA-N 0.000 description 1
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- HITZGLBEZMKWBW-UHFFFAOYSA-N ac1n8rtr Chemical group C1CC2OC2CC1CC[Si](O1)(O2)O[Si](O3)(C4CCCC4)O[Si](O4)(C5CCCC5)O[Si]1(C1CCCC1)O[Si](O1)(C5CCCC5)O[Si]2(C2CCCC2)O[Si]3(C2CCCC2)O[Si]41C1CCCC1 HITZGLBEZMKWBW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- GJTDJAPHKDIQIQ-UHFFFAOYSA-L barium(2+);dinitrite Chemical compound [Ba+2].[O-]N=O.[O-]N=O GJTDJAPHKDIQIQ-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GPBKPJXNAVXOJU-UHFFFAOYSA-N benzene-1,2,4-tricarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C(C(=O)NN)=C1 GPBKPJXNAVXOJU-UHFFFAOYSA-N 0.000 description 1
- IKWQWOFXRCUIFT-UHFFFAOYSA-N benzene-1,2-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C(=O)NN IKWQWOFXRCUIFT-UHFFFAOYSA-N 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical class NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010460 hemp oil Substances 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- DWYKRMTVNUXSIM-UHFFFAOYSA-N hexane-1,6-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCCCCCO DWYKRMTVNUXSIM-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000005597 hydrazone group Chemical group 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 201000006747 infectious mononucleosis Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229940083982 sodium phytate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- HOWFTCIROIVKLW-UHFFFAOYSA-L strontium;dinitrite Chemical compound [Sr+2].[O-]N=O.[O-]N=O HOWFTCIROIVKLW-UHFFFAOYSA-L 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
本発明は、乾燥性に優れ、肉もち感のある光沢を有する塗膜を形成することが可能な硬化型水性樹脂組成物及び該組成物を含んでなる水性塗料組成物に関する。 The present invention relates to a curable aqueous resin composition that is excellent in drying properties and capable of forming a coating film having a glossy texture with a meat feeling, and an aqueous coating composition comprising the composition.
近年、塗料、インキ、接着剤等の分野では、省資源、環境衛生、無公害、非危険物化等の観点から、有機溶剤型の組成物から水性型の組成物への転換が進められている。例えば、水性塗料組成物に使用されるビヒクルとしては、例えば、アルキド樹脂、アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂などの樹脂が挙げられる。これらの水性塗料組成物において、アルキド樹脂は、原材料として不飽和脂肪酸を用いることにより樹脂骨格中に酸化硬化基を導入することができ、それを用いた水性塗料組成物は１液常温硬化が可能となり、また、その油性から、金属面へ塗布された場合の防食性が期待できるが、その軟質な性質が塗膜の乾燥を遅らせ一般的に耐候性に弱さが見られる。他方、アクリル樹脂は、速乾性、耐候性に優れるものの防食性に劣る。これら２種の樹脂の特性を兼備した樹脂水性系材料として、アルキド樹脂とアクリル樹脂を化学反応により結合させるグラフト樹脂などが開発され数多く提案されている。例えば、特許文献１には、ビニルモノマーの重合生成物であるコポリマーと、疎水性のエステル又は部分エステルとを含む水系コポリマー及びその製造方法が提案されている。該公報には、重合時において、モノマー滴以外の第２世代粒子の形成を抑制させるべく、モノマー滴に乾性油酸とポリオールとからの疎水エステルを添加することが提案されている。該公報に記載の水系コポリマーは、揮発性の融合助剤を含まず透明な被膜を形成するが、特に塗布後初期段階において、乾燥性が遅く、形成塗膜の耐候性及び耐水性が十分ではないなどの欠点がある。 In recent years, in the fields of paints, inks, adhesives, etc., from the viewpoint of resource saving, environmental hygiene, non-pollution, non-hazardous materials, etc., conversion from organic solvent type compositions to aqueous type compositions has been promoted. . For example, examples of the vehicle used in the aqueous coating composition include resins such as alkyd resins, acrylic resins, polyester resins, polyurethane resins, and epoxy resins. In these aqueous coating compositions, the alkyd resin can introduce an oxidative curing group into the resin skeleton by using unsaturated fatty acid as a raw material, and the aqueous coating composition using the alkyd resin can be cured at one room temperature. In addition, due to its oiliness, anti-corrosion properties can be expected when applied to a metal surface, but its soft nature delays drying of the coating and generally has a weak weather resistance. On the other hand, the acrylic resin is inferior in anticorrosion property although it is excellent in quick drying property and weather resistance. As an aqueous resin material having the characteristics of these two types of resins, many graft resins and the like for bonding alkyd resins and acrylic resins by chemical reaction have been developed and proposed. For example, Patent Document 1 proposes an aqueous copolymer containing a copolymer, which is a polymerization product of a vinyl monomer, and a hydrophobic ester or partial ester, and a method for producing the same. In this publication, it is proposed to add a hydrophobic ester from a dry oil acid and a polyol to the monomer droplets in order to suppress the formation of second generation particles other than the monomer droplets during the polymerization. The water-based copolymer described in the publication forms a transparent film that does not contain a volatile coalescing aid. However, particularly in the initial stage after application, the drying property is slow, and the formed coating film has insufficient weather resistance and water resistance. There are disadvantages such as not.
本発明の目的は、良好な仕上がり外観を示し、耐候性、耐水性に優れた塗膜を常温でも形成できる硬化型水性樹脂組成物を提供することである。 An object of the present invention is to provide a curable aqueous resin composition that exhibits a good finished appearance and can form a coating film excellent in weather resistance and water resistance even at room temperature.
本発明者らは、今回、特定の製造方法により製造される水性脂肪酸変性樹脂分散体及びカルボニル基を含有する水性樹脂分散体及びヒドラジン誘導体を含む硬化型水性樹脂組成物により本発明を完成するに至った。 The present inventors have now completed the present invention with an aqueous fatty acid-modified resin dispersion produced by a specific production method, an aqueous resin dispersion containing a carbonyl group, and a curable aqueous resin composition containing a hydrazine derivative. It came.
かくして、本発明は、
１．
（Ａ）脂肪酸（ａ１）をエポキシ基含有重合性不飽和モノマー（ａ２）と反応させることにより得られる脂肪酸変性重合性不飽和モノマー（ａ）及び脂肪酸変性重合性不飽和モノマー（ａ）以外のその他の重合性不飽和モノマー（ｂ）を含み、
その他の重合性不飽和モノマー（ｂ）が、酸基含有重合性不飽和モノマー（ｂ１）と、炭素数が４以上の直鎖状、分岐状もしくは環状で飽和又は不飽和の炭化水素基を含有する重合性不飽和モノマー（ｂ２）と、ならびに他の重合性不飽和モノマー（ｂ７）とを含んでなり、他の重合性不飽和モノマー（ｂ７）が、モノマー（ａ）、モノマー（ｂ１）及びモノマー（ｂ２）以外の重合性不飽和モノマーであって、
モノマー（ａ）及びモノマー（ｂ）の合計重量に基づいて、モノマー（ａ）を５〜５０重量％、モノマー（ｂ１）を０．１〜５重量％、モノマー（ｂ２）を４５〜８０重量％及び他の重合性不飽和モノマー（ｂ７）を０〜４９．９重量％含有し、ここで炭素数４以上の炭化水素基を含有する重合性不飽和モノマー（ｂ２）が、炭素数６以上の直鎖状もしくは分岐状の炭化水素基を有する重合性不飽和モノマー（ｂ３）を、モノマー（ａ）及びモノマー（ｂ）の合計重量に基づいて、１〜３０重量％の範囲内で含んでなる
モノマー混合物を水性媒体中に平均粒子径が５００ｎｍ以下になるように微分散させ、得られる乳化物を重合することにより製造される水性脂肪酸変性樹脂分散体、（Ｂ）分散体（Ａ）以外であって、ヒドラジン誘導体（Ｃ）と架橋反応可能なカルボニル基を含有する水性樹脂分散体ならびに（Ｃ）ヒドラジン誘導体を含有し、樹脂（Ａ）と樹脂（Ｂ）の配合比が、固形分重量比で１０／９０〜９０／１０の範囲内、ヒドラジン誘導体（Ｃ）の配合量が樹脂（Ａ）及び樹脂（Ｂ）の合計の樹脂固形分を基準にして、０．０１〜１０重量％にある硬化型水性樹脂組成物、
２．
重合性不飽和モノマー（ｂ２）が、シクロアルキル基含有重合性不飽和モノマー（ｂ４）をさらに含んでなる１項に記載の硬化型水性樹脂組成物、
３．
重合性不飽和モノマー（ｂ２）が、シクロアルキル基含有重合性不飽和モノマー（ｂ４）と、芳香族ビニルモノマー（ｂ５）をさらに含んでなる１項に記載の硬化型水性樹脂組成物、
４．
その他の重合性不飽和モノマー（ｂ）が、ヒドラジン誘導体（Ｃ）と架橋反応可能なカルボニル基含有重合性不飽和モノマー（ｂ６）をさらに含んでなる１項ないし３項のいずれか１項に記載の硬化型水性樹脂組成物、
５．
１項ないし４項のいずれか１項に記載の硬化型水性樹脂組成物を含む水性塗料組成物、
６．
被塗面に、５項に記載の水性塗料組成物を塗装することを特徴とする塗装方法、
７．
６項に記載の方法により得られた塗装物品、に関する。
Thus, the present invention
1.
(A) Other than fatty acid-modified polymerizable unsaturated monomer (a) and fatty acid-modified polymerizable unsaturated monomer (a) obtained by reacting fatty acid (a1) with epoxy group-containing polymerizable unsaturated monomer (a2) A polymerizable unsaturated monomer (b)
The other polymerizable unsaturated monomer (b) contains an acid group-containing polymerizable unsaturated monomer (b1) and a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 4 or more carbon atoms. A polymerizable unsaturated monomer (b2), and other polymerizable unsaturated monomer (b7), wherein the other polymerizable unsaturated monomer (b7) comprises monomer (a), monomer (b1) and A polymerizable unsaturated monomer other than the monomer (b2),
Based on the total weight of monomer (a) and monomer (b), monomer (a) is 5 to 50% by weight, monomer (b1) is 0.1 to 5% by weight, and monomer (b2) is 45 to 80% by weight. And 0 to 49.9% by weight of other polymerizable unsaturated monomer (b7), wherein the polymerizable unsaturated monomer (b2) containing a hydrocarbon group having 4 or more carbon atoms is 6 or more carbon atoms. The polymerizable unsaturated monomer (b3) having a linear or branched hydrocarbon group is included in the range of 1 to 30% by weight based on the total weight of the monomer (a) and the monomer (b). An aqueous fatty acid-modified resin dispersion produced by finely dispersing a monomer mixture in an aqueous medium so that the average particle size is 500 nm or less and polymerizing the resulting emulsion, (B) dispersion ( be other than a), a hydrazine derivative It contains an aqueous resin dispersion and (C) hydrazine derivative containing C) and crosslinkable group, compounding ratio of the resin (A) and the resin (B), by solids weight ratio 10 / 90-90 / 10, within a range of 0.01 to 10% by weight, based on the total resin solid content of the resin (A) and the resin (B), the hydrazine derivative (C) content is curable aqueous resin composition ,
2.
The curable aqueous resin composition according to 1, wherein the polymerizable unsaturated monomer (b 2 ) further comprises a cycloalkyl group-containing polymerizable unsaturated monomer (b4),
3.
The curable aqueous resin composition according to 1, wherein the polymerizable unsaturated monomer (b 2 ) further comprises a cycloalkyl group-containing polymerizable unsaturated monomer (b4) and an aromatic vinyl monomer (b5),
4).
The other polymerizable unsaturated monomer (b) further comprises a carbonyl group-containing polymerizable unsaturated monomer (b6) capable of undergoing a crosslinking reaction with the hydrazine derivative (C). Curable aqueous resin composition,
5.
An aqueous coating composition comprising the curable aqueous resin composition according to any one of items 1 to 4,
6).
A coating method characterized by coating the surface to be coated with the water-based coating composition according to Item 5,
7).
The present invention relates to a coated article obtained by the method according to item 6.
本発明の硬化型水性樹脂組成物によれば、貯蔵安定性、造膜性などに優れ、１液型でありながら乾燥性が良好であり常温でも容易に硬化させることができ、しかも、形成される塗膜は透明性、光沢、仕上り性（肉持ち感）に優れ、耐水性、耐久性、耐食性、耐候性等の性能にも優れているという顕著な効果を奏するものである。 According to the curable aqueous resin composition of the present invention, it is excellent in storage stability, film-forming property, etc., and has a good drying property while being a one-component type, and can be easily cured at room temperature. The coating film exhibits excellent effects such as excellent transparency, gloss, finish (feeling of fleshiness), and excellent performance such as water resistance, durability, corrosion resistance, and weather resistance.
水性脂肪酸変性樹脂分散体（Ａ）
本発明において使用される脂肪酸変性重合性不飽和モノマー（ａ）は、水性脂肪酸変性樹脂分散体（Ａ）を安定に製造させることができ、最終的に得られる硬化型水性樹脂組成物を用いて形成される塗膜に肉もち感を付与し、且つ本発明の組成物に酸化硬化性を付与させる場合において水性脂肪酸変性樹脂分散体（Ａ）粒子に酸化硬化基を導入することができるものであり、脂肪酸由来の炭化水素鎖の末端に重合性不飽和基を有する重合性不飽和モノマーが包含される。ここで、重合性不飽和基としては、例えば、ビニル基、（メタ）アクリロイル基などを挙げることができ、特に（メタ）アクリロイル基が好適である。
Aqueous fatty acid-modified resin dispersion (A)
The fatty acid-modified polymerizable unsaturated monomer (a) used in the present invention can stably produce the aqueous fatty acid-modified resin dispersion (A), and uses the finally obtained curable aqueous resin composition. In the case of imparting a feeling of meat to the formed coating film and imparting oxidative curability to the composition of the present invention, it is possible to introduce an oxidative curing group into the aqueous fatty acid-modified resin dispersion (A) particles. Yes, a polymerizable unsaturated monomer having a polymerizable unsaturated group at the end of a hydrocarbon chain derived from a fatty acid is included. Here, examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is particularly preferable.
脂肪酸変性重合性不飽和モノマー（ａ）としては、例えば、脂肪酸（ａ１）をエポキシ基含有重合性不飽和モノマー（ａ２）又は水酸基含有重合性不飽和モノマー（ａ３）と反応させることにより得られるものを挙げることができる。 Examples of the fatty acid-modified polymerizable unsaturated monomer (a) are those obtained by reacting a fatty acid (a1) with an epoxy group-containing polymerizable unsaturated monomer (a2) or a hydroxyl group-containing polymerizable unsaturated monomer (a3). Can be mentioned.
脂肪酸（ａ１）としては、炭化水素鎖の末端にカルボキシル基が結合した構造を有しているものが挙げられ、例えば、乾性油脂肪酸、半乾性油脂肪酸、不乾性油脂肪酸を挙げることができる。乾性油脂肪酸及び半乾性油脂肪酸は、厳密に区別できるものではないが、通常、乾性油脂肪酸はヨウ素化が１３０以上の不飽和脂肪酸であり、半乾性油脂肪酸はヨウ素化が１００以上かつ１３０未満の不飽和脂肪酸である。他方、不乾性油脂肪酸は、通常、ヨウ素価が１００未満である脂肪酸である。 Examples of the fatty acid (a1) include those having a structure in which a carboxyl group is bonded to the end of a hydrocarbon chain, and examples thereof include a dry oil fatty acid, a semi-dry oil fatty acid, and a non-dry oil fatty acid. Dry oil fatty acids and semi-dry oil fatty acids are not strictly distinguishable, but usually dry oil fatty acids are unsaturated fatty acids that are iodinated 130 or more, and semi-dry oil fatty acids are iodinated 100 or more and less than 130. Of unsaturated fatty acids. On the other hand, non-drying oil fatty acids are usually fatty acids having an iodine value of less than 100.
乾性油脂肪酸及び半乾性油脂肪酸としては、例えば、魚油脂肪酸、脱水ヒマシ油脂肪酸、サフラワー油脂肪酸、亜麻仁油脂肪酸、大豆油脂肪酸、ゴマ油脂肪酸、ケシ油脂肪酸、エノ油脂肪酸、麻実油脂肪酸、ブドウ核油脂肪酸、トウモロコシ油脂肪酸、トール油脂肪酸、ヒマワリ油脂肪酸、綿実油脂肪酸、クルミ油脂肪酸、ゴム種油脂肪酸、ハイジエン酸脂肪酸等が挙げられ、また、不乾性油脂肪酸としては、例えば、ヤシ油脂肪酸、水添ヤシ油脂肪酸、パーム油脂肪酸等が挙げられる。これらは単独でもしくは２種以上組み合わせて使用することができる。さらに、これらの脂肪酸は、カプロン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等と併用することができる。 Examples of the dry oil fatty acid and the semidry oil fatty acid include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hemp oil fatty acid, grape Nuclear oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, hydienoic acid fatty acid, etc., and non-drying oil fatty acid include, for example, coconut oil fatty acid , Hydrogenated coconut oil fatty acid, palm oil fatty acid and the like. These can be used alone or in combination of two or more. Furthermore, these fatty acids can be used in combination with caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like.
脂肪酸変性重合性不飽和モノマー（ａ）を製造するために上記脂肪酸（ａ１）と反応させうるエポキシ基含有重合性不飽和モノマー（ａ２）としては、１分子中に１個のエポキシ基と１個の重合性不飽和基を有する化合物が包含され、具体的には例えば、グリシジル（メタ）アクリレート、β一メチルグリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、３，４−エポキシシクロヘキシルエチル（メタ）アクリレート、３，４−エポキシシクロヘキシルプロピル（メタ）アクリレート、アリルグリシジルエーテル等が挙げられる。これらは単独でもしくは２種以上組み合わせて使用することができる。 The epoxy group-containing polymerizable unsaturated monomer (a2) that can be reacted with the fatty acid (a1) to produce the fatty acid-modified polymerizable unsaturated monomer (a) is one epoxy group and one in one molecule. Specifically, for example, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4- Examples thereof include epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether. These can be used alone or in combination of two or more.
上記脂肪酸（ａ１）とエポキシ基含有重合性不飽和モノマー（ａ２）は、脂肪酸（ａ１）中のカルボキシル基とエポキシ基含有モノマー（ａ２）中のエポキシ基との当量比が０．７５：１〜１．２５：１、好ましくは０．８：１〜１．２：１の範囲内となるような割合で反応させることができる。 The fatty acid (a1) and the epoxy group-containing polymerizable unsaturated monomer (a2) have an equivalent ratio of a carboxyl group in the fatty acid (a1) and an epoxy group in the epoxy group-containing monomer (a2) of 0.75: 1 to 1. The reaction can be carried out in such a ratio that it is in the range of 1.25: 1, preferably 0.8: 1 to 1.2: 1.
上記脂肪酸（ａ１）とエポキシ基含有重合性不飽和モノマー（ａ２）との反応は、通常、重合禁止剤の存在下に、ゲル化などの反応上の問題を起こすことなく、脂肪酸成分中のカルボキシル基とエポキシ基含有重合性不飽和モノマー中のエポキシ基とが円滑に反応できる条件下で行うことができ、通常、約１００〜約１８０℃の温度で約０．５〜約１０時間加熱することにより行うのが適している。 The reaction between the fatty acid (a1) and the epoxy group-containing polymerizable unsaturated monomer (a2) is usually carried out in the presence of a polymerization inhibitor without causing a problem such as gelation in the fatty acid component. The reaction can be carried out under conditions that allow the group and the epoxy group in the epoxy group-containing polymerizable unsaturated monomer to react smoothly, and is usually heated at a temperature of about 100 to about 180 ° C. for about 0.5 to about 10 hours. Is suitable.
この反応において、Ｎ，Ｎ−ジメチルアミノエタノール等の３級アミン、臭化テトラエチルアンモニウム、臭化テトラブチルアンモニウム等の４級アンモニウム塩等のエステル化反応触媒を用いることができ、さらに、反応に対して不活性な有機溶剤を使用してもよい。 In this reaction, an esterification reaction catalyst such as a tertiary amine such as N, N-dimethylaminoethanol, a quaternary ammonium salt such as tetraethylammonium bromide or tetrabutylammonium bromide can be used. An inert organic solvent may be used.
上記重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ピロカテコール、ｐ−ｔｅｒｔ−ブチルカテコールなどのヒドロキシ化合物；ニトロベンゼン、ニトロ安息香酸、ｏ−，ｍ−又はｐ−ジニトロベンゼン、２，４−ジニトロトルエン、２，４−ジニトロフェノール、トリニトロベンゼン、ピクリン酸などのニトロ化合物；ｐ−ベンゾキノン、ジクロロベンゾキノン、クロルアニル、アンスラキノン、フェナンスロキノンなどのキノン化合物；ニトロソベンゼン、ニトロソ−β−ナフトールなどのニトロソ化合物等のそれ自体既知のラジカル重合禁止剤が挙げられ、これらは単独でもしくは２種以上組み合わせて使用することができる。 Examples of the polymerization inhibitor include hydroxy compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and p-tert-butylcatechol; nitrobenzene, nitrobenzoic acid, o-, m- or p-dinitrobenzene, 2,4- Nitro compounds such as dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene, and picric acid; quinone compounds such as p-benzoquinone, dichlorobenzoquinone, chloranil, anthraquinone, and phenanthroquinone; nitrosobenzene, nitroso-β-naphthol, and the like Examples thereof include radical polymerization inhibitors known per se such as nitroso compounds, and these can be used alone or in combination of two or more.
また、脂肪酸変性重合性モノマー（ａ）は、上記脂肪酸（ａ１）を水酸基含有重合性不飽和モノマー（ａ３）とエステル化反応させることによっても得ることができる。かかる水酸基含有重合性不飽和モノマー（ａ３）としては、１分子中に１個の水酸基と１個の重合性不飽和基を有する化合物が包含され、具体的には例えば、２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、３−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどの（メタ）アクリル酸のＣ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレート、アリルアルコ−ル、上記Ｃ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレートのε−カプロラクトン変性体などの水酸基を有する（メタ）アクリレート；分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等が挙げられ、これらは単独でもしくは２種以上組み合わせて使用することができる。 The fatty acid-modified polymerizable monomer (a) can also be obtained by esterifying the fatty acid (a1) with the hydroxyl group-containing polymerizable unsaturated monomer (a3). Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a3) include a compound having one hydroxyl group and one polymerizable unsaturated group in one molecule. Specifically, for example, 2-hydroxyethyl (meta C2-C8 hydroxyalkyl (meth) acrylate of (meth) acrylic acid such as acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol -(Meth) acrylate having a hydroxyl group, such as an ε-caprolactone modified product of the above C2-C8 hydroxyalkyl (meth) acrylate; (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end, and the like. These can be used alone or in combination of two or more. .
上記脂肪酸（ａ１）と水酸基含有重合性不飽和モノマー（ａ３）は、通常、該脂肪酸（ａ１）中のカルボキシル基対水酸基含有モノマー（ａ３）中の水酸基との当量比が０．４：１〜１．２５：１、好ましくは０．５：１〜１．２：１の範囲内となるような割合で反応させることができる。 The fatty acid (a1) and the hydroxyl group-containing polymerizable unsaturated monomer (a3) usually have an equivalent ratio of 0.4: 1 to the carboxyl group in the fatty acid (a1) to the hydroxyl group in the hydroxyl group-containing monomer (a3). The reaction can be carried out in such a ratio that it is in the range of 1.25: 1, preferably 0.5: 1 to 1.2: 1.
上記脂肪酸（ａ１）と水酸基含有重合性不飽和モノマー（ａ３）との反応は、通常、重合禁止剤の存在下に、ゲル化などの反応上の問題を起こすことなく、脂肪酸（ａ１）成分中のカルボキシル基と水酸基含有重合性不飽和モノマー中の水酸基とが円滑に反応できる条件下で行うことができ、通常、エステル化触媒の存在下に、約１００〜約１８０℃の温度で約０．５〜約１０時間加熱することにより行うのが適している。エステル化触媒としては、例えば、硫酸、硫酸アルミニウム、硫酸水素カリウム、アルキル置換ベンゼン、塩酸、硫酸メチル、リン酸等が挙げられ、これらの触媒は、通常、反応させる上記脂肪酸（ａ１）と水酸基含有重合性不飽和モノマー（ａ３）の合計量を基準にして、約０．００１〜約２．０重量％の範囲内で使用することができる。さらに、反応に対して不活性な有機溶剤を使用することもできる。 The reaction between the fatty acid (a1) and the hydroxyl group-containing polymerizable unsaturated monomer (a3) is usually carried out in the fatty acid (a1) component in the presence of a polymerization inhibitor without causing a reaction problem such as gelation. In the presence of an esterification catalyst at a temperature of about 100 to about 180 ° C. in the presence of an esterification catalyst. It is suitable to carry out by heating for 5 to about 10 hours. Examples of the esterification catalyst include sulfuric acid, aluminum sulfate, potassium hydrogen sulfate, alkyl-substituted benzene, hydrochloric acid, methyl sulfate, phosphoric acid, and the like. These catalysts usually contain the fatty acid (a1) to be reacted and a hydroxyl group. It can be used in the range of about 0.001 to about 2.0% by weight, based on the total amount of the polymerizable unsaturated monomer (a3). Furthermore, an organic solvent inert to the reaction can also be used.
上記重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ピロカテコール、ｐ−ｔｅｒｔ−ブチルカテコールなどのヒドロキシ化合物；ニトロベンゼン、ニトロ安息香酸、ｏ−，ｍ−又はｐ−ジニトロベンゼン、２，４−ジニトロトルエン、２，４−ジニトロフェノール、トリニトロベンゼン、ピクリン酸などのニトロ化合物；ｐ−ベンゾキノン、ジクロロベンゾキノン、クロルアニル、アンスラキノン、フェナンスロキノンなどのキノン化合物；ニトロソベンゼン、ニトロソ−β−ナフトールなどのニトロソ化合物等のそれ自体既知のラジカル重合禁止剤が挙げられ、これらは単独でもしくは２種以上組み合わせて使用することができる。 Examples of the polymerization inhibitor include hydroxy compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and p-tert-butylcatechol; nitrobenzene, nitrobenzoic acid, o-, m- or p-dinitrobenzene, 2,4- Nitro compounds such as dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene, and picric acid; quinone compounds such as p-benzoquinone, dichlorobenzoquinone, chloranil, anthraquinone, and phenanthroquinone; nitrosobenzene, nitroso-β-naphthol, and the like Examples thereof include radical polymerization inhibitors known per se such as nitroso compounds, and these can be used alone or in combination of two or more.
重合性不飽和モノマー（ｂ）
本発明における水性脂肪酸変性樹脂分散体（Ａ）において、その他の重合性不飽和モノマー（ｂ）は、上記脂肪酸変性重合性不飽和モノマー（ａ）と共重合可能な重合性不飽和モノマーであり、分子中に１個以上好ましくは１個の重合性不飽和基を含有する化合物を挙げることができる。重合性不飽和基としては、ビニル基及び（メタ）アクリロイル基が挙げられ、その他の重合性不飽和モノマー（ｂ）として具体的には、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、トリデシル（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、「イソステアリルアクリレート」（大阪有機化学社製）、シクロヘキシル（メタ）アクリレ−ト、メチルシクロヘキシル（メタ）アクリレ−ト、ｔ−ブチルシクロヘキシル（メタ）アクリレ−ト、シクロドデシル（メタ）アクリレ−ト等のアルキル又はシクロアルキル（メタ）アクリレート；イソボルニル（メタ）アクリレート等のイソボルニル基を有する重合性不飽和モノマー；アダマンチル（メタ）アクリレート等のアダマンチル基を有する重合性不飽和モノマー；グリシジル（メタ）アクリレート、β−メチルグリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、３，４−エポキシシクロヘキシルエチル（メタ）アクリレート、３，４−エポキシシクロヘキシルプロピル（メタ）アクリレート、アリルグリシジルエーテル等のエポキシ基を有する重合性不飽和モノマー；スチレン、α−メチルスチレン、ビニルトルエンなどの芳香族ビニルモノマー；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、γ−（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリエトキシシランなどのアルコキシシリル基を有する重合性不飽和モノマー；ポリジメチルシロキサンマクロモノマー等のシロキサンマクロモノマー；パーフルオロブチルエチル（メタ）アクリレート、パーフルオロオクチルエチル（メタ）アクリレート等のパーフルオロアルキル（メタ）アクリレート；フルオロオレフィン等のアルキルフッ素基を有する重合性不飽和モノマー；マレイミド基等の光重合性官能基を有する重合性不飽和モノマー；Ｎ−ビニルピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニル等のビニル化合物；（メタ）アクリル酸、フマル酸、イタコン酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレート等のカルボキシル基を有する重合性不飽和モノマー；無水マレイン酸、無水イタコン酸等の不飽和カルボン酸無水物；（メタ）アクリロニトリル、（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、さらにグリシジル（メタ）アクリレートとアミン類との付加物等の含窒素重合性不飽和モノマー；２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、３−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどの（メタ）アクリル酸の炭素数２〜８個の水酸基を有するアルキル（メタ）アクリレート、アリルアルコ−ル、上記炭素数２〜８のヒドロキシ（メタ）アクリレートのε−カプロラクトン変性体などの水酸基を有する（メタ）アクリレート；分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等の水酸基を有する重合性不飽和モノマー：分子末端がアルコキシ基であるポリオキシエチレン鎖を有する（メタ）アクリレート；２−アクリルアミド−２−メチルプロパンスルホン酸、アリルスルホン酸、スチレンスルホン酸ナトリウム塩、スルホエチルメタクリレート及びそのナトリウム塩やアンモニウム塩等のスルホン酸基を有する重合性不飽和モノマー；２−ヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２−ヒドロキシ−４−（３−アクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２，２'−ジヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２，２'−ジヒドロキシ−４−（３−アクリルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノンなど２，４−ジヒドロキシベンゾフェノン、２，２'，４−トリヒドロキシベンゾフェノンなどのヒドロキシベンゾフェノン類とグリシジル（メタ）アクリレートとの付加反応生成物、或いは２−（２'−ヒドロキシ−５'−メタクリロイルオキシエチルフェニル）−２Ｈ−ベンゾトリアゾール等の紫外線吸収性官能基を有する重合性不飽和モノマー；４−（メタ）アクリロイルオキシ−１，２，２，６，６−ペンタメチルピペリジン、４−（メタ）アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルアミノ−２，２，６，６−テトラメチルピペリジン、１−クロトノイル−４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン等の紫外線安定性重合性不飽和モノマー；アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、４〜７個の炭素原子を有するビニルアルキルケトン（例えばビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等のカルボニル基を有する重合性不飽和モノマー；アリル（メタ）アクリレ−ト、エチレングリコ−ルジ（メタ）アクリレ−ト、トリエチレングリコ−ルジ（メタ）アクリレ−ト、テトラエチレングリコ−ルジ（メタ）アクリレ−ト、１，３−ブチレングリコ−ルジ（メタ）アクリレ−ト、トリメチロ−ルプロパントリ（メタ）アクリレ−ト、１，４−ブタンジオ−ルジ（メタ）アクリレ−ト、ネオペンチルグリコ−ルジ（メタ）アクリレ−ト、１，６−ヘキサンジオ−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルテトラ（メタ）アクリレ−ト、グリセロ−ルジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタンジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタントリ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルプロパントリ（メタ）アクリレ−ト、トリアリルイソシアヌレ−ト、ジアリルテレフタレ−ト、ジビニルベンゼン等の１分子中に少なくとも２個の重合性不飽和基を有する多ビニル化合物等；等が挙げられ、これらは所望の性能に応じて単独でもしくは２種以上を適宜使用される。
Polymerizable unsaturated monomer (b)
In the aqueous fatty acid-modified resin dispersion (A) in the present invention, the other polymerizable unsaturated monomer (b) is a polymerizable unsaturated monomer copolymerizable with the fatty acid-modified polymerizable unsaturated monomer (a), Examples of the compound include one or more, preferably one polymerizable unsaturated group in the molecule. Examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group. Specific examples of the other polymerizable unsaturated monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n -Propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meta ) Acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.), cyclohexyl ( (Meta) acrylate Alkyl or cycloalkyl (meth) acrylate such as methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, etc .; having isobornyl group such as isobornyl (meth) acrylate Polymerizable unsaturated monomer; polymerizable unsaturated monomer having an adamantyl group such as adamantyl (meth) acrylate; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, Polymerizable unsaturated monomers having an epoxy group such as 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; styrene, α- Aromatic vinyl monomers such as styrene styrene and vinyl toluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyl Polymerizable unsaturated monomer having alkoxysilyl group such as triethoxysilane; Siloxane macromonomer such as polydimethylsiloxane macromonomer; Perfluoroalkyl such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate ( (Meth) acrylate; polymerizable unsaturated monomer having alkyl fluorine group such as fluoroolefin; polymerizable unsaturated monomer having photopolymerizable functional group such as maleimide group; N-vinyl pyro Polymers having a carboxyl group such as (meth) acrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, etc., vinyl compounds such as don, ethylene, butadiene, chloroprene, vinyl propionate and vinyl acetate Unsaturated monomers; unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; (meth) acrylonitrile, (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, and glycidyl (meta ) Nitrogen-containing polymerizable unsaturated monomers such as adducts of acrylates and amines; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Hydroxybutyl (Meth) acrylate and other (meth) acrylic acid alkyl (meth) acrylates having 2 to 8 carbon hydroxyl groups, allyl alcohol, and ε-caprolactone modified products of the above-mentioned 2 to 8 hydroxy (meth) acrylates (Meth) acrylate having a hydroxyl group such as; polymerizable unsaturated monomer having a hydroxyl group such as (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end: having a polyoxyethylene chain having an alkoxy group at the molecular end (Meth) acrylate; 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid sodium salt, sulfoethyl methacrylate and polymerizable unsaturated monomer having a sulfonic acid group such as sodium salt and ammonium salt thereof; 2 -Hydroxy-4- (3-meta Liloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, Hydroxybenzophenones such as 2,2'-dihydroxy-4- (3-acryloxy-2-hydroxypropoxy) benzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone and glycidyl (meth) acrylate Or a polymerizable unsaturated monomer having an ultraviolet-absorbing functional group such as 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole; 4- (meth) acryloyl Oxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloylamino-2, 2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6- UV-stable polymerizable unsaturated monomers such as tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine; A carbonyl group such as Lorraine, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) Polymerizable unsaturated monomer having: allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate 1,6-hexanediol (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethyl Ethanedi (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate, 1,1,1-trishydroxymethylpropanetri (meth) acrylate, triallyl isocyanurate Multi-vinyl compounds having at least two polymerizable unsaturated groups in one molecule, such as benzoyl, diallyl terephthalate, divinylbenzene, and the like. These may be used alone or in combination depending on the desired performance. The above is used appropriately.
上記モノマー（ａ）及びモノマー（ｂ）の使用割合は、特に制限されるものではなく、目的とする硬化型水性樹脂組成物に望まれる性能や用途などに応じて適宜選択することができるが、一般には、モノマー（ａ）及びモノマー（ｂ）の合計量を基準にして、モノマー（ａ）は５〜５０重量％、好ましくは１０〜４０重量％、さらに好ましくは１０〜３５重量％の範囲内、そしてモノマー（ｂ）は５０〜９５重量％、好ましくは６０〜９０重量％、さらに好ましくは６５〜９０重量％の範囲内とすることができる。モノマー（ａ）の使用割合が５重量％未満では、本発明の硬化型水性樹脂組成物を用いて形成される塗膜の酸化硬化が十分に進行せず、また、塗膜の肉持ち感が損なわれることがあり、他方、５０重量％を越えると、塗膜が脆くなり、耐候性が不十分になることがある。 The use ratio of the monomer (a) and the monomer (b) is not particularly limited and can be appropriately selected according to the performance and application desired for the target curable aqueous resin composition. Generally, the monomer (a) is in the range of 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 10 to 35% by weight, based on the total amount of monomer (a) and monomer (b). , And monomer (b) can be in the range of 50-95 wt%, preferably 60-90 wt%, more preferably 65-90 wt%. When the proportion of the monomer (a) used is less than 5% by weight, the oxidative curing of the coating film formed using the curable aqueous resin composition of the present invention does not proceed sufficiently, and the coating film has a feeling of fleshiness. On the other hand, if it exceeds 50% by weight, the coating film becomes brittle and the weather resistance may be insufficient.
上記他の重合性不飽和モノマー（ｂ）としては、使用する全モノマー（ｂ）の（共）重合体の理論ガラス転移温度が０〜１００℃、好ましくは１０〜８０℃、さらに好ましくは４０〜７０℃の範囲内となるように選択することが望ましい。 As said other polymerizable unsaturated monomer (b), the theoretical glass transition temperature of the (co) polymer of all the monomers (b) to be used is 0-100 degreeC, Preferably it is 10-80 degreeC, More preferably, it is 40- It is desirable to select such that it is within the range of 70 ° C.
本発明において、ガラス転移温度（絶対温度）は、下記式により算出される値である。 In the present invention, the glass transition temperature (absolute temperature) is a value calculated by the following formula.
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。なお、各モノマーのホモポリマーのガラス転移温度は、Polymer Hand Book (Second Edition,J.Brandrup・E.H.Immergut 編)による値であり、該文献に記載されていないモノマーのガラス転移温度は、該モノマーのホモポリマーを重量平均分子量が５万程度になるようにして合成し、そのガラス転移温度を示差走査型熱分析により測定したときの値を使用する。
1 / Tg = W1 / T1 + W2 / T2 + ... Wn / Tn
In the formula, W1, W2... Wn is% by weight of each monomer [= (blending amount of each monomer / total weight of monomer) × 100], and T1, T2... Tn are glass transition temperatures (absolute Temperature). The glass transition temperature of the homopolymer of each monomer is a value according to Polymer Hand Book (Second Edition, edited by J. Brandrup / EHImmergut), and the glass transition temperature of a monomer not described in this document is the homopolymer of the monomer. The polymer is synthesized so that the weight average molecular weight is about 50,000, and the value when the glass transition temperature is measured by differential scanning thermal analysis is used.
使用する全モノマー（ｂ）の（共）重合体の理論ガラス転移温度が上記範囲内となるようにすることにより、硬化型水性樹脂組成物を用いて形成される塗膜のの造膜性、耐候性、耐水性等の塗膜物性とを両立させることができる。 By making the theoretical glass transition temperature of the (co) polymer of all monomers (b) to be used within the above range, the film-forming property of the coating film formed using the curable aqueous resin composition, It is possible to achieve both coating film properties such as weather resistance and water resistance.
また、他の重合性不飽和モノマー（ｂ）は、酸基含有重合性不飽和モノマー（ｂ１）を、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして、０．１〜５重量％、好ましくは０．５重量％以上で且つ３重量％未満の範囲内で含んでなることが望ましい。 The other polymerizable unsaturated monomer (b) is an acid group-containing polymerizable unsaturated monomer (b1) based on the total weight of the monomer (a) and the monomer (b). %, Preferably 0.5% by weight or more and less than 3% by weight.
酸基含有重合性不飽和モノマー（ｂ１）としては、例えば、（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレート等のカルボキシル基を有する重合性不飽和モノマー；２−アクリルアミド−２−メチルプロパンスルホン酸、アリルスルホン酸、スチレンスルホン酸ナトリウム塩、スルホエチルメタクリレート及びそのナトリウム塩やアンモニウム塩等のスルホン酸基を有する重合性不飽和モノマー等を挙げることができ、特に、アクリル酸、メタクリル酸、クロトン酸が好適である。 Examples of the acid group-containing polymerizable unsaturated monomer (b1) include polymerizable unsaturated monomers having a carboxyl group such as (meth) acrylic acid, maleic acid, crotonic acid, and β-carboxyethyl acrylate; 2-acrylamide-2 -Methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid sodium salt, sulfoethyl methacrylate and polymerizable unsaturated monomers having a sulfonic acid group such as sodium salt and ammonium salt thereof, in particular, acrylic acid, Methacrylic acid and crotonic acid are preferred.
他の重合性不飽和モノマー（ｂ）の少なくとも一部として酸基含有重合性不飽和モノマー（ｂ１）を使用することにより、得られる水性脂肪酸変性樹脂分散体（Ａ）粒子の水性媒体中における安定性や機械安定性を確保することができ、また、それを含有する硬化型水性樹脂組成物をエナメル塗料に適用した場合において、塗料の調色性を向上させることができる。 By using the acid group-containing polymerizable unsaturated monomer (b1) as at least a part of the other polymerizable unsaturated monomer (b), the aqueous fatty acid-modified resin dispersion (A) particles obtained can be stabilized in an aqueous medium. Property and mechanical stability can be ensured, and when the curable aqueous resin composition containing the same is applied to an enamel paint, the toning property of the paint can be improved.
また、他の重合性不飽和モノマー（ｂ）は、その少なくとも一部として、炭素数が４以上の直鎖状、分岐状もしくは環状で飽和又は不飽和の炭化水素基を含有する重合性不飽和モノマー（ｂ２）を、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして、３０〜９０重量％、好ましくは３５〜８５重量％、さらに好ましくは４５〜８０重量％の範囲内で含んでなることが望ましい。 In addition, the other polymerizable unsaturated monomer (b) contains, as at least a part thereof, a polymerizable unsaturated monomer containing a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 4 or more carbon atoms. Monomer (b2) is included in the range of 30 to 90% by weight, preferably 35 to 85% by weight, more preferably 45 to 80% by weight, based on the total weight of monomer (a) and monomer (b). It is desirable that
炭素数が４以上の直鎖状、分岐状もしくは環状で飽和又は不飽和の炭化水素基を含有する重合性不飽和モノマー（ｂ２）としては、例えば、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、トリデシル（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、「イソステアリルアクリレート」（大阪有機化学社製）、シクロヘキシル（メタ）アクリレ−ト、メチルシクロヘキシル（メタ）アクリレ−ト、ｔ−ブチルシクロヘキシル（メタ）アクリレ−ト、シクロドデシル（メタ）アクリレ−ト等のアルキル又はシクロアルキル（メタ）アクリレート；イソボルニル（メタ）アクリレート等のイソボルニル基を有する重合性不飽和化合物；アダマンチル（メタ）アクリレート等のアダマンチル基を有する重合性不飽和化合物；スチレン、α−メチルスチレン、ビニルトルエンなどのビニル芳香族化合物等を挙げることができる。かかる炭素数が４以上の炭化水素基を有する重合性不飽和モノマー（ｂ２）の使用により、硬化型水性樹脂組成物を用いて形成される塗膜の耐水性を向上させることができる。 Examples of the polymerizable unsaturated monomer (b2) containing a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 4 or more carbon atoms include n-butyl (meth) acrylate and i-butyl. (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) ) Acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.), cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, Cyclododecyl (meth) acrylate, etc. Alkyl or cycloalkyl (meth) acrylate; polymerizable unsaturated compound having an isobornyl group such as isobornyl (meth) acrylate; polymerizable unsaturated compound having an adamantyl group such as adamantyl (meth) acrylate; styrene, α-methylstyrene, And vinyl aromatic compounds such as vinyl toluene. The use of the polymerizable unsaturated monomer (b2) having a hydrocarbon group having 4 or more carbon atoms can improve the water resistance of a coating film formed using the curable aqueous resin composition.
また、他の重合性不飽和モノマー（ｂ）は、その少なくとも一部として、炭素数が６以上の直鎖状もしくは分岐状の炭化水素基を含有する重合性不飽和モノマー（ｂ３）を、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして、１〜３０重量％、好ましくは５〜２０重量％、さらに好ましくは６〜１８重量％含んでなることが望ましい。 In addition, the other polymerizable unsaturated monomer (b) includes, as at least a part thereof, a polymerizable unsaturated monomer (b3) containing a linear or branched hydrocarbon group having 6 or more carbon atoms. It is desirable to contain 1 to 30% by weight, preferably 5 to 20% by weight, more preferably 6 to 18% by weight, based on the total weight of (a) and monomer (b).
炭素数が６以上の直鎖状もしくは分岐状の炭化水素基を含有する重合性不飽和モノマー（ｂ３）としては、例えば、ｎ−ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、トリデシル（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、「イソステアリルアクリレート」（大阪有機化学社製）等を挙げることができ、これらは単独でまたは２種以上組み合わせて使用することができる。 Examples of the polymerizable unsaturated monomer (b3) containing a linear or branched hydrocarbon group having 6 or more carbon atoms include n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl ( And (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.), etc. Or in combination of two or more.
他の重合性不飽和モノマー（ｂ）の少なくとも一部として、炭素数が６以上の直鎖状もしくは分岐状の炭化水素基を含有する重合性不飽和モノマー（ｂ３）を使用することにより、水性脂肪酸変性樹脂分散体（Ａ）の製造において該他の重合性不飽和モノマー（ｂ）を脂肪酸変性重合性不飽和モノマー（ａ）と共に微粒化した場合におけるモノマー乳化物の重合安定性を保持することができ、しかも、硬化型水性樹脂組成物を用いて形成される塗膜の耐水性を向上させることができる。 By using the polymerizable unsaturated monomer (b3) containing a linear or branched hydrocarbon group having 6 or more carbon atoms as at least a part of the other polymerizable unsaturated monomer (b), aqueous Maintaining the polymerization stability of the monomer emulsion when the other polymerizable unsaturated monomer (b) is atomized together with the fatty acid-modified polymerizable unsaturated monomer (a) in the production of the fatty acid-modified resin dispersion (A). Moreover, the water resistance of the coating film formed using the curable aqueous resin composition can be improved.
他の重合性不飽和モノマー（ｂ）は、酸基含有重合性不飽和モノマー（ｂ１）と、炭素数が４以上の直鎖状、分岐状もしくは環状で飽和又は不飽和の炭化水素基を含有する重合性不飽和モノマー（ｂ２）と、ならびに脂肪酸変性重合性不飽和モノマー（ａ）、上記モノマー（ｂ１）及びモノマー（ｂ２）以外の他の重合性不飽和モノマー（ｂ７）とを含んでなり、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして、モノマー（ａ）を５〜５０重量％、好ましくは１０〜４０重量％、さらに好ましくは１０〜３５重量％、モノマー（ｂ１）を０．１〜５重量％、好ましくは０．５〜４．５重量％、さらに好ましくは０．５〜３重量％、モノマー（ｂ２）を４５〜８０重量％、好ましくは５０〜７５重量％、さらに好ましくは５５〜７０重量％、及び他の重合性不飽和モノマー（ｂ７）を０〜４９．９重量％、好ましくは０〜３９．５重量％、さらに好ましくは０〜３４．５重量％含有し、ここで炭素数が４以上の炭化水素基を含有する重合性不飽和モノマー（ｂ２）が上記炭素数が６以上の直鎖状もしくは分岐状の炭化水素基を含有する重合性不飽和モノマー（ｂ３）を、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして１〜３０重量％、好ましくは５〜２０重量％、さらに好ましくは６〜１８重量％の範囲内で含んでなることが望ましい。 The other polymerizable unsaturated monomer (b) contains an acid group-containing polymerizable unsaturated monomer (b1) and a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 or more carbon atoms. A polymerizable unsaturated monomer (b2), and a fatty acid-modified polymerizable unsaturated monomer (a), and another polymerizable unsaturated monomer (b7) other than the monomer (b1) and the monomer (b2). , Based on the total weight of monomer (a) and monomer (b), monomer (a) is 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 10 to 35% by weight, monomer (b1) 0.1 to 5% by weight, preferably 0.5 to 4.5% by weight, more preferably 0.5 to 3% by weight, and monomer (b2) 45 to 80% by weight, preferably 50 to 75% by weight. , More preferably 55-7 0 to 49.9 wt%, preferably 0 to 39.5 wt%, more preferably 0 to 34.5 wt% of other polymerizable unsaturated monomer (b7), wherein the number of carbon atoms A polymerizable unsaturated monomer (b3) containing a hydrocarbon group having 4 or more hydrocarbon groups, a polymerizable unsaturated monomer (b3) containing a linear or branched hydrocarbon group having 6 or more carbon atoms, It is desirable to comprise within the range of 1 to 30% by weight, preferably 5 to 20% by weight, more preferably 6 to 18% by weight, based on the total weight of (a) and monomer (b).
上記の場合において、モノマー（ａ）の使用割合が５重量％未満では、本発明の硬化型水性樹脂組成物を用いて形成される塗膜の肉もち感が不十分になり、反対に５０重量％を超えると、塗膜の耐候性が不十分になることがある。また、モノマー（ｂ１）の使用割合が０．１重量％未満では、水性脂肪酸変性樹脂分散体（Ａ）の粒子の安定性が不十分となることがあり、反対に５重量％を超えると、硬化型水性樹脂組成物を用いて形成される塗膜の耐水性が低下することがある。さらに、モノマー（ｂ２）の使用割合が４５重量％未満では、硬化型水性樹脂組成物を用いて形成される塗膜の耐水性が低下することがあり、他方、８０重量％を超えると、水性脂肪酸変性樹脂分散体（Ａ）粒子の貯蔵安定性の低下に伴い、硬化型水性樹脂組成物の貯蔵安定性が低下することがある。 In the above case, when the proportion of the monomer (a) used is less than 5% by weight, the feeling of meat of the coating film formed using the curable aqueous resin composition of the present invention becomes insufficient, and on the contrary, 50% by weight. When it exceeds%, the weather resistance of the coating film may be insufficient. Further, when the proportion of the monomer (b1) used is less than 0.1% by weight, the stability of the particles of the aqueous fatty acid-modified resin dispersion (A) may be insufficient. The water resistance of the coating film formed using the curable aqueous resin composition may be lowered. Furthermore, if the proportion of the monomer (b2) used is less than 45% by weight, the water resistance of the coating film formed using the curable aqueous resin composition may be lowered. As the storage stability of the fatty acid-modified resin dispersion (A) particles decreases, the storage stability of the curable aqueous resin composition may decrease.
上記特定割合の脂肪酸変性重合性不飽和モノマー（ａ）及びその他の重合性不飽和モノマー（ｂ）を共重合させることにより、水性脂肪酸変性樹脂分散体（Ａ）を安定に製造することができ、しかも、硬化型水性樹脂組成物を用いて形成される塗膜の透明感、肉もち感があり、耐水性等の性能を向上させることができる。 By copolymerizing the above-mentioned specific proportion of the fatty acid-modified polymerizable unsaturated monomer (a) and other polymerizable unsaturated monomer (b), the aqueous fatty acid-modified resin dispersion (A) can be stably produced, In addition, the coating film formed using the curable aqueous resin composition has a feeling of transparency and a feeling of meat, and can improve performance such as water resistance.
また、その他の重合性不飽和モノマー（ｂ）は、その少なくとも一部として、シクロアルキル基含有重合性不飽和モノマー（ｂ４）を含んでなることが望ましい。シクロアルキル基含有重合性不飽和モノマー（ｂ４）としては、１分子中に１個の炭素数が６以上のシクロアルキル基と１個の重合性不飽和結合を有する化合物が好適であり、例えば、シクロヘキシル（メタ）アクリレ−ト、メチルシクロヘキシル（メタ）アクリレ−ト、ｔ−ブチルシクロヘキシル（メタ）アクリレ−ト、シクロドデシル（メタ）アクリレ−ト等を挙げることができ、これらは単独で又は２種以上組み合わせて使用することができる。中でも、シクロヘキシル（メタ）アクリレートが好適である。 Further, the other polymerizable unsaturated monomer (b) preferably contains the cycloalkyl group-containing polymerizable unsaturated monomer (b4) as at least a part thereof. As the cycloalkyl group-containing polymerizable unsaturated monomer (b4), a compound having one cycloalkyl group having 6 or more carbon atoms and one polymerizable unsaturated bond in one molecule is suitable. Examples thereof include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, and the like. These can be used in combination. Of these, cyclohexyl (meth) acrylate is preferred.
その他の重合性不飽和モノマー（ｂ）の少なくとも一部として、シクロアルキル基含有重合性不飽和モノマー（ｂ４）を含んでなるものを使用することにより、硬化型水性樹脂組成物を用いて形成される塗膜の耐候性を向上させることができ、また、耐水性、耐汚染性等も改善することができる。耐候性向上を目的とする場合のその含有量は、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして、１〜７０重量％、好ましくは１０〜６０重量％、さらに好ましくは２５〜４５重量％の範囲内が好適である。 It is formed by using a curable aqueous resin composition by using one comprising the cycloalkyl group-containing polymerizable unsaturated monomer (b4) as at least a part of the other polymerizable unsaturated monomer (b). The weather resistance of the coating film can be improved, and the water resistance, stain resistance and the like can also be improved. The content in the case of improving the weather resistance is 1 to 70% by weight, preferably 10 to 60% by weight, more preferably 25 to 25% based on the total weight of the monomer (a) and the monomer (b). A range of 45% by weight is preferred.
また、その他の重合性不飽和モノマー（ｂ）は、その少なくとも一部として、芳香族ビニルモノマー（ｂ５）を含んでなることが望ましい。芳香族ビニルモノマー（ｂ５）としては、例えば、スチレン、α−メチルスチレン、ビニルトルエンなどのビニル芳香族化合物を挙げることができ、これらは単独で又は２種以上組み合わせて使用することができる。かかる芳香族ビニルモノマー（ｂ５）の使用により、モノマー（ａ）及びモノマー（ｂ）の共重合性を高めることができ、未反応のモノマーを最小限にすることができ、そして耐水性など形成塗膜の物性を向上させることができる。 Further, the other polymerizable unsaturated monomer (b) desirably contains an aromatic vinyl monomer (b5) as at least a part thereof. As an aromatic vinyl monomer (b5), vinyl aromatic compounds, such as styrene, (alpha) -methylstyrene, vinyl toluene, can be mentioned, for example, These can be used individually or in combination of 2 or more types. By using such an aromatic vinyl monomer (b5), the copolymerizability of the monomer (a) and the monomer (b) can be increased, the amount of unreacted monomers can be minimized, and water-resistant coating such as water resistance can be formed. The physical properties of the film can be improved.
該芳香族ビニルモノマー（ｂ５）は、一般に、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして、１〜５０重量％、好ましくは５〜４５重量％、さらに好ましくは１２〜３５重量％の範囲内で使用するのが好適である。 The aromatic vinyl monomer (b5) is generally 1 to 50% by weight, preferably 5 to 45% by weight, more preferably 12 to 35% by weight, based on the total weight of the monomer (a) and the monomer (b). It is preferable to use within the range of%.
本発明の硬化型組成物を用いて形成される塗膜に耐候性を付与させる場合などにおいては、その他の重合性不飽和モノマー（ｂ）は、シクロアルキル基含有重合性不飽和モノマー（ｂ４）と、芳香族ビニルモノマー（ｂ５）と、ならびにモノマー（ａ）、モノマー（ｂ４）及びモノマー（ｂ５）以外の重合性不飽和モノマー（ｂ８）とを含んでなり、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして、モノマー（ａ）を５〜５０重量％、好ましくは１０〜４０重量％、さらに好ましくは１０〜３５重量％、モノマー（ｂ４）を１〜７０重量％、好ましくは１０〜６０重量％、さらに好ましくは２５〜４５重量％、モノマー（ｂ５）を１〜５０重量％、好ましくは５〜４５重量％、さらに好ましくは１２〜３５重量％、及び他の重合性不飽和モノマー（ｂ８）を０〜９３重量％、好ましくは０〜７５重量％、さらに好ましくは０〜４７重量％含有することが望ましい。 In the case where weather resistance is imparted to the coating film formed using the curable composition of the present invention, the other polymerizable unsaturated monomer (b) is a cycloalkyl group-containing polymerizable unsaturated monomer (b4). And an aromatic vinyl monomer (b5), and a polymerizable unsaturated monomer (b8) other than the monomer (a), the monomer (b4) and the monomer (b5), and the monomer (a) and the monomer (b ) Based on the total weight of the monomer (a), 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 10 to 35% by weight, and monomer (b4) 1 to 70% by weight, preferably 10-60 wt%, more preferably 25-45 wt%, monomer (b5) 1-50 wt%, preferably 5-45 wt%, more preferably 12-35 wt%, and other polymerizations Unsaturated monomer (b8) 0 to 93 wt%, preferably 0-75 wt%, still more preferably contains 0-47 wt%.
この場合において、モノマー（ａ）の使用割合が５重量％未満では、本発明の硬化型水性樹脂組成物を用いて形成される塗膜の肉もち感が不十分になり、反対に５０重量％を超えると、硬化型水性樹脂組成物を用いて形成される塗膜の耐候性が低下することがあり、また、モノマー（ｂ４）の使用割合が１重量％未満では、形成される塗膜の耐候性が不十分であり、一方７０重量％を超えると、水性脂肪酸変性樹脂分散体（Ａ）の重合安定性が不十分となることがある。さらに、モノマー（ｂ５）の使用割合が１重量％未満では、形成される塗膜の耐水性が低下することがあり、他方、５０重量％を超えると、形成塗膜の耐候性が不十分となることがある。 In this case, when the proportion of the monomer (a) used is less than 5% by weight, the feeling of meat of the coating film formed using the curable aqueous resin composition of the present invention becomes insufficient. When the amount exceeds 50%, the weather resistance of the coating film formed using the curable aqueous resin composition may be reduced. When the proportion of the monomer (b4) used is less than 1% by weight, The weather resistance is insufficient. On the other hand, if it exceeds 70% by weight, the polymerization stability of the aqueous fatty acid-modified resin dispersion (A) may be insufficient. Furthermore, if the proportion of the monomer (b5) used is less than 1% by weight, the water resistance of the formed coating film may be lowered. On the other hand, if it exceeds 50% by weight, the weather resistance of the formed coating film is insufficient. May be.
上記特定割合の脂肪酸変性重合性不飽和モノマー（ａ）及びその他の重合性不飽和モノマー（ｂ）を共重合させることにより、硬化型水性樹脂組成物を用いて形成される塗膜が透明感、肉もち感があり、しかも耐水性、耐候性等に優れることができる。 By coating the above-mentioned specific proportion of the fatty acid-modified polymerizable unsaturated monomer (a) and other polymerizable unsaturated monomer (b), the coating film formed using the curable aqueous resin composition is transparent, It has a meaty feeling and can be excellent in water resistance, weather resistance and the like.
また、その他の重合性不飽和モノマー（ｂ）は、その少なくとも一部として、カルボニル基含有重合性不飽和モノマー（ｂ６）を含んでなることが望ましい。 Further, the other polymerizable unsaturated monomer (b) preferably contains the carbonyl group-containing polymerizable unsaturated monomer (b6) as at least a part thereof.
カルボニル基含有重合性不飽和モノマー（ｂ６）としては、１分子中に1個のカルボニル基と1個の重合性不飽和結合を有する化合物が包含され、具体的には例えば、アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、４〜７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等が挙げられ、これらは単独で又は２種以上組み合わせて使用することができる。中でも、特にダイアセトン（メタ）アクリルアミドが好適である。 Examples of the carbonyl group-containing polymerizable unsaturated monomer (b6) include compounds having one carbonyl group and one polymerizable unsaturated bond in one molecule, such as acrolein and diacetone acrylamide. , Diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like. Or it can use in combination of 2 or more types. Of these, diacetone (meth) acrylamide is particularly preferred.
その他の重合性不飽和モノマー（ｂ）の少なくとも一部として、カルボニル基含有重合性不飽和モノマー（ｂ６）を含んでなるものを使用し且つ後述のヒドラジン誘導体を配合せしめることにより、カルボニル基とヒドラジン誘導体との架橋を進行させることができ、塗膜の乾燥性をより一層向上させることができ、耐候性、耐水性等の物性にも優れた塗膜を形成する塗料組成物を調製することができる。 By using at least a part of the other polymerizable unsaturated monomer (b) containing the carbonyl group-containing polymerizable unsaturated monomer (b6) and blending a hydrazine derivative described later, a carbonyl group and hydrazine It is possible to proceed with crosslinking with the derivative, to further improve the drying property of the coating film, and to prepare a coating composition that forms a coating film having excellent physical properties such as weather resistance and water resistance. it can.
かかるカルボニル基含有重合性不飽和モノマー（ｂ６）は、一般に、モノマー（ａ）及びモノマー（ｂ）の合計重量を基準にして、０．５〜３５重量％、好ましくは２〜２０重量％の範囲内で使用するのが適している。 Such carbonyl group-containing polymerizable unsaturated monomer (b6) is generally in the range of 0.5 to 35% by weight, preferably 2 to 20% by weight, based on the total weight of monomer (a) and monomer (b). Suitable for use within.
また、その他の重合性不飽和モノマー（ｂ）は、水性脂肪酸変性樹脂分散体（Ａ）における重合段階又は貯蔵段階における粒子の安定性を確保するために、水酸基含有（メタ）アクリレートを含んでなることもできる。水酸基含有(メタ)アクリレートとしては、前記で例示したものが挙げられ、その使用割合は、一般に、モノマー（ａ）及びモノマー（ｂ）の合計量を基準にして、１〜５０重量％、好ましくは１〜３０重量％、さらに好ましくは１〜１０重量％の範囲内とすることができる。 The other polymerizable unsaturated monomer (b) comprises a hydroxyl group-containing (meth) acrylate in order to ensure the stability of the particles in the polymerization stage or storage stage in the aqueous fatty acid-modified resin dispersion (A). You can also. Examples of the hydroxyl group-containing (meth) acrylate include those exemplified above, and the use ratio thereof is generally 1 to 50% by weight, preferably based on the total amount of the monomer (a) and the monomer (b), preferably It can be in the range of 1 to 30% by weight, more preferably 1 to 10% by weight.
本発明において、上記水性脂肪酸変性樹脂分散体（Ａ）は、脂肪酸変性重合性不飽和モノマー（ａ）とその他の重合性不飽和モノマー（ｂ）を含むモノマー混合物を水性媒体中に平均粒子径が５００ｎｍ以下、平均粒子径が５０〜５００ｎｍ、特に７５〜４００ｎｍ、さらに特に１００〜２５０ｎｍの範囲内となるように微分散させ、得られる乳化物を重合することにより製造されるものである。 In the present invention, the aqueous fatty acid-modified resin dispersion (A) has an average particle size of a monomer mixture containing a fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b) in an aqueous medium. It is produced by polymerizing the emulsion obtained by finely dispersing it to 500 nm or less and having an average particle size in the range of 50 to 500 nm, particularly 75 to 400 nm, more particularly 100 to 250 nm.
上記製造方法により、水性脂肪酸変性樹脂分散体（Ａ）が安定に製造でき、該樹脂分散体（Ａ）を含む硬化型水性樹脂組成物を用いて形成される塗膜は造膜性に優れ、良好な仕上がり性、耐水性を有することができる。 By the above production method, the aqueous fatty acid-modified resin dispersion (A) can be stably produced, and the coating film formed using the curable aqueous resin composition containing the resin dispersion (A) has excellent film-forming properties. It can have good finish and water resistance.
上記モノマー混合物は、さらに、実質的に重合性不飽和基を含有しない化合物を含有することもでき、これにより、水性脂肪酸変性樹脂分散体（Ａ）粒子が、該化合物を内包することもできる。 The monomer mixture may further contain a compound that does not substantially contain a polymerizable unsaturated group, whereby the aqueous fatty acid-modified resin dispersion (A) particles can include the compound.
かかる実質的に重合性不飽和基を含有しない化合物としては、例えば、紫外線吸収剤、紫外線安定剤及び金属ドライヤー等の塗料用添加剤；イソシアネート化合物、ブロックイソシアネート化合物、メラミンなどの硬化剤；アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、アルキド樹脂、ポリオルガノシロキサン等の樹脂；顔料、染料等の着色剤等を挙げることができる。 Examples of such a compound that does not substantially contain a polymerizable unsaturated group include, for example, UV absorbers, UV stabilizers and additives for coating materials such as metal dryers; curing agents such as isocyanate compounds, blocked isocyanate compounds, and melamines; acrylic resins And resins such as polyester resins, polyurethane resins, alkyd resins, polyorganosiloxanes; colorants such as pigments and dyes.
上記モノマー混合物は、水性媒体に微分散するに際して、必要に応じて、乳化剤を併用してもよい。該乳化剤としては、アニオン系乳化剤、ノニオン系乳化剤が好適であり、該アニオン性乳化剤としては、例えば、アルキルスルホン酸、アルキルベンゼンスルホン酸、アルキルリン酸などのナトリウム塩やアンモニウム塩が挙げられ、また、ノニオン系乳化剤としては、例えば、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシエチレンフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレート、ポリオキシエチレンモノオレエート、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタンモノステアレート、ソルビタントリオレート、ポリオキシエチレンソルビタンモノラウレート等が挙げられる。 When the monomer mixture is finely dispersed in an aqueous medium, an emulsifier may be used in combination as necessary. As the emulsifier, an anionic emulsifier and a nonionic emulsifier are suitable. Examples of the anionic emulsifier include sodium salts and ammonium salts such as alkylsulfonic acid, alkylbenzenesulfonic acid, and alkylphosphoric acid. Nonionic emulsifiers include, for example, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl Phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monos Areto, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, and the like.
また、１分子中にアニオン性基とポリオキシエチレン基やポリオキシプロピレン基等のポリオキシアルキレン基を有するポリオキシアルキレン基含有アニオン性乳化剤や、１分子中に該アニオン性基と重合性不飽和基とを有する反応性アニオン性乳化剤を使用してもよい。 Also, a polyoxyalkylene group-containing anionic emulsifier having an anionic group and a polyoxyalkylene group such as a polyoxyethylene group or a polyoxypropylene group in one molecule, or the anionic group and polymerizable unsaturated in one molecule Reactive anionic emulsifiers having groups may be used.
該乳化剤は使用される全モノマーの合計量を基準にして０．１〜１５重量％、好ましくは０．５〜１２重量％の範囲内で使用することができる。 The emulsifier can be used in the range of 0.1 to 15% by weight, preferably 0.5 to 12% by weight, based on the total amount of all monomers used.
また、モノマー混合物は、得られる水性脂肪酸変性樹脂分散体（Ａ）の分子量を調整する目的で、連鎖移動剤を含んでいてもよい。該連鎖移動剤としては、メルカプト基を有する化合物が包含され、具体的には例えば、ラウリルメルカプタン、ｔ−ドデシルメルカプタン、オクチルメルカプタン、チオグリコール酸２−エチルへキシル、２−メチル−５−ｔｅｒｔ−ブチルチオフェノール、メルカプトエタノ−ル、チオグリセロ−ル、メルカプト酢酸（チオグリコ−ル酸）、メルカプトプロピオネート、ｎ−オクチル−３−メルカプトプロピオネート等が挙げられる。該連鎖移動剤の使用量は、一般に、全モノマーの合計量を基準にして、０．０５〜１０重量％、特に０．１〜５重量％の範囲内が好適である。 Moreover, the monomer mixture may contain a chain transfer agent for the purpose of adjusting the molecular weight of the obtained aqueous fatty acid-modified resin dispersion (A). Examples of the chain transfer agent include compounds having a mercapto group. Specifically, for example, lauryl mercaptan, t-dodecyl mercaptan, octyl mercaptan, 2-ethylhexyl thioglycolate, 2-methyl-5-tert- Examples thereof include butylthiophenol, mercaptoethanol, thioglycerol, mercaptoacetic acid (thioglycolic acid), mercaptopropionate, and n-octyl-3-mercaptopropionate. In general, the chain transfer agent is preferably used in an amount of 0.05 to 10% by weight, particularly 0.1 to 5% by weight, based on the total amount of all monomers.
本発明の脂肪酸変性樹脂分散体（Ａ）は、上記脂肪酸変性重合性不飽和モノマー（ａ）等により、重合段階においてモノマー（ｂ）の拡散を抑制することができ、安定に製造されるものであるが、必要に応じてモノマー混合物に、ヘキサデカン等の長鎖飽和炭化水素系溶剤、ヘキサデカノール等の長鎖アルコール系溶剤等の一般にミニエマルション重合で使用される疎水性有機溶剤を配合してもよい。 The fatty acid-modified resin dispersion (A) of the present invention can be stably produced by the fatty acid-modified polymerizable unsaturated monomer (a) and the like so that diffusion of the monomer (b) can be suppressed in the polymerization stage. However, if necessary, a hydrophobic organic solvent generally used in miniemulsion polymerization such as a long-chain saturated hydrocarbon solvent such as hexadecane or a long-chain alcohol solvent such as hexadecanol may be added to the monomer mixture. Also good.
以上に述べたモノマー混合物は水性媒体中に微分散させることによりモノマー乳化物が形成せしめられる。 The monomer mixture described above is finely dispersed in an aqueous medium to form a monomer emulsion.
上記モノマー混合物の水性媒体中における濃度は、形成されるモノマー乳化物の微粒化適性、重合段階における安定性、水性塗料に適用したときの実用性などの観点から、一般に、１０〜７０重量％、好ましくは２０〜６０重量％の範囲内が好適である。 The concentration of the monomer mixture in the aqueous medium is generally 10 to 70% by weight from the viewpoint of atomization suitability of the monomer emulsion to be formed, stability in the polymerization stage, practicality when applied to an aqueous paint, A range of 20 to 60% by weight is preferable.
モノマー混合物の水性媒体中への微分散は、通常、高エネルギーせん断能力を有する分散機を用いて行うことができる。その際に使用しうる該分散機としては、例えば、高圧乳化装置、超音波乳化機、高圧コロイドミル、高圧ホモジナイザー等が挙げられる。これらの分散機は、通常、１０〜１０００ＭＰａ、好ましくは５０〜３００ＭＰａ程度の高圧下で操作することができる。また、該機械にて分散を行う前に、該モノマー混合物をあらかじめディスパー等で予備乳化してもよい。 The fine dispersion of the monomer mixture in the aqueous medium can be usually performed using a disperser having a high energy shearing ability. Examples of the disperser that can be used in this case include a high-pressure emulsifier, an ultrasonic emulsifier, a high-pressure colloid mill, and a high-pressure homogenizer. These dispersers can usually be operated under a high pressure of about 10 to 1000 MPa, preferably about 50 to 300 MPa. In addition, the monomer mixture may be pre-emulsified with a disper or the like in advance before being dispersed by the machine.
モノマー混合物を上記手法により水性媒体中に微分散させることにより得られるモノマー乳化物中の分散粒子の平均粒子径は、形成塗膜の透明性、耐水性等の点から、５００ｎｍ以下、好ましくは８０〜４００ｎｍ、さらに好ましくは１００〜３００ｎｍの範囲内が適している。 The average particle size of the dispersed particles in the monomer emulsion obtained by finely dispersing the monomer mixture in the aqueous medium by the above method is 500 nm or less, preferably 80 from the viewpoint of the transparency of the formed coating film, water resistance, and the like. The range of ˜400 nm, more preferably 100 to 300 nm is suitable.
かくして得られるモノマー乳化物の重合は、例えば、ミニエマルション重合法に従い、微分散後のモノマー乳化物を撹拌機を備えた反応器に全量仕込み、重合開始剤を添加し、攪拌しながら加熱することにより行うことができる。 In the polymerization of the monomer emulsion thus obtained, for example, in accordance with the mini-emulsion polymerization method, all the monomer emulsion after fine dispersion is charged into a reactor equipped with a stirrer, a polymerization initiator is added, and the mixture is heated while stirring. Can be performed.
上記重合開始剤としては、油溶性、水溶性のいずれのタイプのものであってもよく、油溶性の重合開始剤としては、例えば、ベンゾイルパーオキシド、オクタノイルパーオキサイド、ラウロイルパーオキシド、ステアロイルパーオキサイド等の有機過酸化物；アゾビスイソブチロニトリル、アゾビス（２，４−ジメチルバレロニトリル）等のアゾ化合物等が挙げられ、また、水溶性の開始剤としては、例えば、クメンハイドロパーオキサイド、ｔｅｒｔ−ブチルパーオキサイド、ｔｅｒｔ−ブチルパーオキシラウレート、 ｔｅｒｔ−ブチルパーオキシイソプロピルカーボネート、 ｔｅｒｔ−ブチルパーオキシアセテート、ジイソプロピルベンゼンハイドロパーオキサイド等の有機過酸化物；アゾビス（２−メチルプロピオンニトリル）、アゾビス（２−メチルブチロニトリル）、４、４'−アゾビス（４−シアノブタン酸）、ジメチルアゾビス（２−メチルプロピオネート）、アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）−プロピオンアミド］、アゾビス｛２−メチル−Ｎ−［２−（１−ヒドロキシブチル）］−プロピオンアミド｝等のアゾ化合物；過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩等が挙げられる。これらはそれぞれ単独でもしくは２種以上組み合わせて用いることができる。また、上記重合開始剤に、必要に応じて、糖、ナトリウムホルムアルデヒドスルホキシレート、鉄錯体等の還元剤を併用し、レドックス重合系としてもよい。 The polymerization initiator may be either oil-soluble or water-soluble, and examples of the oil-soluble polymerization initiator include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide. Organic peroxides such as oxides; azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile); and water-soluble initiators such as cumene hydroperoxide , Organic peroxides such as tert-butyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide; azobis (2-methylpropiononitrile) A Bis (2-methylbutyronitrile), 4,4′-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl)- Azo compounds such as propionamide] and azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}; and persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate. . These can be used alone or in combination of two or more. Further, if necessary, a reducing agent such as sugar, sodium formaldehyde sulfoxylate, or iron complex may be used in combination with the polymerization initiator to form a redox polymerization system.
上記重合開始剤の使用量は、一般に、モノマー（Ａ）及びモノマー（Ｂ）の合計重量を基準にして、０．１〜５重量％、特に０．２〜３重量％の範囲内が好ましい。該重合開始剤の添加方法は、特に制限されるものではなく、その種類や量などに応じて適宜選択することができる。例えば、予めモノマー混合物（Ｉ）又は水性媒体に含ませてもよく、或いは重合時に一括して添加してもよく又は滴下してもよい。 In general, the amount of the polymerization initiator used is preferably in the range of 0.1 to 5% by weight, particularly 0.2 to 3% by weight, based on the total weight of the monomer (A) and the monomer (B). The method for adding the polymerization initiator is not particularly limited, and can be appropriately selected according to the type and amount thereof. For example, it may be previously contained in the monomer mixture (I) or the aqueous medium, or may be added all at once during the polymerization, or may be dropped.
本発明においては、得られる水性脂肪酸変性樹脂分散体（Ａ）の粒子の機械的安定性を向上させるために、該水性脂肪酸変性樹脂分散体（Ａ）が酸性基を有する場合には、これを中和剤により中和することが望ましい。該中和剤としては、酸性基を中和できるものであれば特に制限はなく、例えば、水酸化ナトリウム、水酸化カリウム、トリメチルアミン、ジメチルアミノエタノール、２−メチル−２−アミノ−１−プロパノール、トリエチルアミン、アンモニア水などが挙げられ、これらの中和剤は、中和後の水性樹脂分散体のｐＨが６．５〜９．０程度となるような量で用いることが望ましい。 In the present invention, in order to improve the mechanical stability of the particles of the resulting aqueous fatty acid-modified resin dispersion (A), when the aqueous fatty acid-modified resin dispersion (A) has an acidic group, It is desirable to neutralize with a neutralizing agent. The neutralizing agent is not particularly limited as long as it can neutralize acidic groups. For example, sodium hydroxide, potassium hydroxide, trimethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, Examples thereof include triethylamine and aqueous ammonia, and these neutralizing agents are desirably used in such an amount that the pH of the aqueous resin dispersion after neutralization is about 6.5 to 9.0.
上記水性脂肪酸変性樹脂分散体（Ａ）は、硬化型水性樹脂組成物を用いて形成される塗膜の耐候性、耐水性及び仕上がり性の点から、一般に、１万〜５０万、特に３〜２０万の範囲内の重量平均分子量を有することが望ましい。ここで、重量平均分子量は、溶媒としてテトラヒドロフランを使用し、ゲルパーミュエーションクロマトグラフィにより測定した分子量をポリスチレンの分子量を基準にして換算した値である。該ゲルパーミュエーションクロマトグラフィに用いるカラムとしては、「ＴＳＫｇｅｌ Ｇ−４０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−３０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−２５００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−２０００Ｈ×Ｌ」（いずれも東ソー（株）社製）を挙げることができる。
また、水性脂肪酸変性樹脂分散体（Ａ）において、分散樹脂の平均粒子径は、分散樹脂の平均粒子径が５００ｎｍ以下、特に１００〜３００ｎｍの範囲内にすることができる。
The aqueous fatty acid-modified resin dispersion (A) is generally from 10,000 to 500,000, particularly from 3 to 500,000 in terms of the weather resistance, water resistance and finish of the coating film formed using the curable aqueous resin composition. It is desirable to have a weight average molecular weight in the range of 200,000. Here, the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography based on the molecular weight of polystyrene using tetrahydrofuran as a solvent. Columns used in the gel permeation chromatography are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (all Tosoh Corporation).
In the aqueous fatty acid-modified resin dispersion (A), the average particle size of the dispersed resin can be within the range of 500 nm or less, particularly 100 to 300 nm, as the average particle size of the dispersed resin.
カルボニル基を含有する水性樹脂分散体（Ｂ）
本発明の硬化型水性樹脂組成物に含有されるカルボニル基を含有する水性樹脂分散体（Ｂ）は、上記水性脂肪酸変性樹脂分散体（Ａ）以外の樹脂であって、カルボニル基を有する重合性不飽和モノマー（ｃ）及びその他の重合性不飽和モノマー（ｄ）を含む重合性不飽和モノマー混合物を共重合して得られる樹脂であり、該樹脂（Ｂ）中のカルボニル基は後述のヒドラジン誘導体と架橋反応して、本発明の硬化型水性樹脂組成物から形成される塗膜の耐水性、耐候性を向上させるために導入されるものである。
Aqueous resin dispersion containing carbonyl group (B)
The aqueous resin dispersion (B) containing a carbonyl group contained in the curable aqueous resin composition of the present invention is a resin other than the aqueous fatty acid-modified resin dispersion (A), and has a carbonyl group-polymerizable property. A resin obtained by copolymerizing a polymerizable unsaturated monomer mixture containing an unsaturated monomer (c) and another polymerizable unsaturated monomer (d), and the carbonyl group in the resin (B) is a hydrazine derivative described later. In order to improve the water resistance and weather resistance of the coating film formed from the curable aqueous resin composition of the present invention by a crosslinking reaction.
上記カルボニル基を含有する水性樹脂分散体（Ｂ）は、本発明の硬化型水性樹脂組成物を用いて形成される塗膜の耐候性の点から、脂肪酸変性重合性不飽和モノマー（ａ）を共重合成分として含有しないことが望ましい。 From the viewpoint of the weather resistance of the coating film formed using the curable aqueous resin composition of the present invention, the aqueous resin dispersion (B) containing the carbonyl group contains a fatty acid-modified polymerizable unsaturated monomer (a). It is desirable not to contain it as a copolymerization component.
上記カルボニル基含有重合性不飽和モノマー（ｃ）としては、水性脂肪酸変性樹脂分散体（Ａ）の説明で列記したカルボニル基含有重合性不飽和モノマー（ｂ６）から１種または２種以上適宜選択して使用できる。該分散体（Ｂ）により、硬化型水性樹脂組成物を用いて形成される塗膜の塗布後の初期段階における耐水性や耐候性を向上させることができる。 The carbonyl group-containing polymerizable unsaturated monomer (c) is appropriately selected from one or more carbonyl group-containing polymerizable unsaturated monomers (b6) listed in the description of the aqueous fatty acid-modified resin dispersion (A). Can be used. With the dispersion (B), it is possible to improve water resistance and weather resistance in an initial stage after application of a coating film formed using the curable aqueous resin composition.
他方、カルボニル基含有重合性不飽和モノマー（ｃ）と共重合されるその他の重合性不飽和モノマー（ｄ）としては、重合性不飽和モノマー（ｂ６）以外の重合性不飽和モノマー（ｂ）から１種または２種以上を適宜選択して使用できる。 On the other hand, as the other polymerizable unsaturated monomer (d) copolymerized with the carbonyl group-containing polymerizable unsaturated monomer (c), the polymerizable unsaturated monomer (b) other than the polymerizable unsaturated monomer (b6) is used. One type or two or more types can be appropriately selected and used.
上記カルボニル基を有する水性樹脂分散体（Ｂ）の製造方法は、特に制限されるものではないが、例えば、一般的な乳化重合法に従い、乳化剤としての界面活性剤の存在下に、上記カルボニル基含有重合性不飽和モノマーを含む重合性不飽和モノマー混合物を共重合することにより容易に製造することができる。 The method for producing the aqueous resin dispersion (B) having a carbonyl group is not particularly limited. For example, according to a general emulsion polymerization method, the carbonyl group is added in the presence of a surfactant as an emulsifier. It can be easily produced by copolymerizing a polymerizable unsaturated monomer mixture containing the containing polymerizable unsaturated monomer.
上記の乳化重合に際して、カルボニル基含有重合性不飽和モノマー（ｃ）及びその他の重合性不飽和モノマー（ｄ）は、モノマー（ｃ）及び（ｄ）の合計重量を基準にして、一般に、カルボニル基含有重合性不飽和モノマー（ｃ）が２〜３０重量％、好ましくは３〜２５重量％、及びその他の重合性不飽和モノマー（ｄ）が７０〜９８重量％、好ましくは７５〜９７重量％の範囲内となるような割合で使用することができる。 In the above emulsion polymerization, the carbonyl group-containing polymerizable unsaturated monomer (c) and the other polymerizable unsaturated monomer (d) are generally carbonyl groups based on the total weight of the monomers (c) and (d). The content of the polymerizable unsaturated monomer (c) is 2 to 30% by weight, preferably 3 to 25% by weight, and the other polymerizable unsaturated monomer (d) is 70 to 98% by weight, preferably 75 to 97% by weight. It can be used at such a ratio that it is within the range.
カルボニル基を含有する水性樹脂分散体（Ｂ）の製造において、使用される乳化剤及び重合開始剤としては、上記水性脂肪酸変性樹脂分散体（Ａ）の説明で列記した乳化剤及び重合開始剤から１種又は２種以上を適宜選択して使用できる。
上記カルボニル基含有水性樹脂分散体（Ｂ）は、一般に５，０００〜１，０００，０００、好ましくは２０，０００〜５００，０００の範囲内の重量平均分子量を有することができる。
In the production of the aqueous resin dispersion (B) containing a carbonyl group, the emulsifier and the polymerization initiator used are one of the emulsifiers and polymerization initiators listed in the description of the aqueous fatty acid-modified resin dispersion (A). Or it can select and use 2 or more types suitably.
The carbonyl group-containing aqueous resin dispersion (B) can generally have a weight average molecular weight in the range of 5,000 to 1,000,000, preferably 20,000 to 500,000.
また、上記水性樹脂分散体（Ｂ）は、例えば、有機溶剤存在下にて上記モノマー（ｃ）及び（ｄ）を共重合させた後、得られる共重合体を中和剤で中和して水溶性化又は水分散化する方法、これをさらに水性媒体中で高エネルギーせん断能力を有する分散機により分散する方法、ミニエマルション重合法等によっても製造することができる。さらに、得られる共重合体の重量平均分子量を調整する目的から、連鎖移動剤の存在下で重合を行ってもよい。 The aqueous resin dispersion (B) is obtained by, for example, copolymerizing the monomers (c) and (d) in the presence of an organic solvent, and then neutralizing the resulting copolymer with a neutralizing agent. It can also be produced by a method of water solubilization or water dispersion, a method of dispersing this in an aqueous medium with a disperser having a high energy shearing ability, a miniemulsion polymerization method, or the like. Furthermore, for the purpose of adjusting the weight average molecular weight of the obtained copolymer, polymerization may be performed in the presence of a chain transfer agent.
ヒドラジン誘導体（Ｃ）
本発明の硬化型水性樹脂組成物においては、ヒドラジン誘導体（Ｃ）を含有する。該誘導体（Ｃ）としては、具体的には、例えば、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、グルタル酸ジヒドラジド、こはく酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等の２〜１８個の炭素原子を有する飽和カルボン酸ジヒドラジド；マレイン酸ジヒドラジド、フマル酸ジヒドラジド、イタコン酸ジヒドラジドなどのモノオレフィン性不飽和ジカルボン酸ジヒドラジド；フタル酸ジヒドラジド、テレフタル酸ジヒドラジドまたはイソフタル酸ジヒドラジド、ピロメリット酸のジヒドラジド、トリヒドラジドまたはテトラヒドラジド；ニトリロトリヒドラジド、クエン酸トリヒドラジド、１，２，４−ベンゼントリヒドラジド、エチレンジアミンテトラ酢酸テトラヒドラジド、１，４，５，８−ナフトエ酸テトラヒドラジド；カルボン酸低級アルキルエステル基を有する低重合体をヒドラジンまたはヒドラジン水化物（ヒドラジンヒドラード）と反応させてなるポリヒドラジド；炭酸ジヒドラジド等のヒドラジド基を有する化合物；ビスセミカルバジド；ヘキサメチレンジイソシアネートやイソホロンジイソシアネート等のジイソシアネート及びそれにより誘導されるポリイソシアネート化合物にＮ，Ｎ−ジメチルヒドラジン等のＮ，Ｎ−置換ヒドラジンや上記例示のヒドラジドを過剰に反応させて得られる多官能セミカルバジド；該ポリイソシアネート化合物とポリエーテルとポリオール類やポリエチレングリコールモノアルキルエーテル類等の親水性基を含む活性水素化合物との反応物中のイソシアネート基に上記例示のジヒドラジドを過剰に反応させて得られる水系多官能セミカルバジド；該多官能セミカルバジドと水系多官能セミカルバジドとの混合物等のセミカルバジド基を有する化合物、ビスアセチルジヒドラゾン等のヒドラゾン基を有する化合物等が挙げられる。
Hydrazine derivative (C)
The curable aqueous resin composition of the present invention contains a hydrazine derivative (C). Specific examples of the derivative (C) include saturated oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and the like. Carboxylic acid dihydrazides; monoolefinic unsaturated dicarboxylic acid dihydrazides such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid dihydrazide, terephthalic acid dihydrazide or isophthalic acid dihydrazide, pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide Nitrilotrihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tet Hydrazide; a polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride); a compound having a hydrazide group such as dihydrazide carbonate; bissemicarbazide; hexamethylene diisocyanate or isophorone A polyfunctional semicarbazide obtained by excessively reacting a diisocyanate such as diisocyanate and a polyisocyanate compound derived therefrom with an N, N-substituted hydrazine such as N, N-dimethylhydrazine or the hydrazide exemplified above; The dihydrazide exemplified above is excessively reacted with an isocyanate group in a reaction product of a polyether and an active hydrogen compound containing a hydrophilic group such as polyols or polyethylene glycol monoalkyl ethers. It was an aqueous polyfunctional semicarbazide obtained is A compound having a semicarbazide group, such as a mixture of polyfunctional semicarbazide and aqueous polyfunctional semicarbazide, compounds and the like having a hydrazone group such as bis-acetyl-di hydrazone.
上記ヒドラジン誘導体（Ｃ）を含有せしめることにより、形成塗膜が空気中の有害物質、例えばホルムアルデヒド等を吸着除去することが可能となり有用であり、また、組成物中のカルボニル基に反応する架橋剤として作用することができる。 By containing the hydrazine derivative (C), the formed coating film is useful because it can adsorb and remove harmful substances in the air, such as formaldehyde, and is also useful as a crosslinking agent that reacts with a carbonyl group in the composition. Can act as
上記ヒドラジン誘導体（Ｃ）の配合量は、脂肪酸変性樹脂分散体（Ａ）及びカルボニル基を有する水性樹脂分散体（Ａ）の合計の樹脂固形分を基準にして、一般に０．０１〜１０重量％、特に０．１〜５重量％の範囲内が望ましい。 The amount of the hydrazine derivative (C) is generally 0.01 to 10% by weight based on the total resin solid content of the fatty acid-modified resin dispersion (A) and the aqueous resin dispersion (A) having a carbonyl group. In particular, the range of 0.1 to 5% by weight is desirable.
硬化型水性樹脂組成物
本発明の硬化型水性樹脂組成物は、上記水性脂肪酸変性樹脂分散体（Ａ）及びカルボニル基含有水性樹脂分散体（Ｂ）及びヒドラジン誘導体を必須成分として含有し、基体樹脂成分として含有される水性脂肪酸変性樹脂分散体（Ａ）及びカルボニル基含有水性樹脂分散体（Ｂ）の配合割合は厳密に制限されるものではなく、該樹脂組成物の用途等に応じて変えることができるが、樹脂（Ａ）／樹脂（Ｂ）の固形分重量比で、一般に１０／９０〜９０／１０、好ましくは２０／８０〜８０／２０の範囲内とすることができる。上記の樹脂（Ａ）／樹脂（Ｂ）の固形分重量比が１０／９０より小さいと、肉もち感のある光沢が得られなくなり、また金属面へ塗布された場合の防食性が劣ることがあり、他方９０／１０を超えると、初期耐水性が劣る可能性がある。
Curable aqueous resin composition The curable aqueous resin composition of the present invention contains the aqueous fatty acid-modified resin dispersion (A), the carbonyl group-containing aqueous resin dispersion (B), and a hydrazine derivative as essential components. However, the blending ratio of the aqueous fatty acid-modified resin dispersion (A) and the carbonyl group-containing aqueous resin dispersion (B) contained as the base resin component is not strictly limited, and is suitable for the use of the resin composition, etc. Depending on the solid content weight ratio of resin (A) / resin (B), it can generally be within the range of 10/90 to 90/10, preferably 20/80 to 80/20. . When the solid content weight ratio of the resin (A) / resin (B) is less than 10/90, a gloss with a meaty feeling cannot be obtained, and the corrosion resistance when applied to a metal surface may be inferior. On the other hand, if it exceeds 90/10, the initial water resistance may be inferior.
水性塗料組成物
本発明の水性塗料組成物は、以上に述べた硬化型水性樹脂組成物を含んでなるものである。
Aqueous paint composition The aqueous paint composition of the present invention comprises the curable aqueous resin composition described above.
上記硬化型水性樹脂組成物を水性塗料組成物に適用した場合においては、クリヤー塗料、エナメル塗料のいずれにも適用できる。 When the curable aqueous resin composition is applied to an aqueous coating composition, it can be applied to either a clear coating or an enamel coating.
エナメル塗料として適用する場合には、顔料分として、従来公知の着色顔料，光輝性顔料、体質顔料、防錆顔料等を配合することができる。 When applied as an enamel paint, conventionally known color pigments, glitter pigments, extender pigments, rust preventive pigments and the like can be blended as the pigment component.
顔料の配合量としては顔料体積濃度で５〜４５％、特に１０〜３５％、さらに特に１４〜３０％の範囲内であることが望ましい。ここで「顔料体積濃度」は、塗料中の全樹脂分と全顔料との合計固形分に占めるその顔料分の体積割合である。本明細書において、顔料の体積を算出する際のもとになる顔料の比重は「塗料原料便覧第６版」（社団法人日本塗料工業会）によるものであり、また、樹脂固形分の比重は１と近似するものとする。 The blending amount of the pigment is desirably in the range of 5 to 45%, particularly 10 to 35%, more particularly 14 to 30% in terms of the pigment volume concentration. Here, the “pigment volume concentration” is a volume ratio of the pigment content in the total solid content of the total resin content and the total pigment content in the paint. In this specification, the specific gravity of the pigment which is the basis for calculating the volume of the pigment is according to “Paint Raw Material Handbook 6th Edition” (Japan Paint Manufacturers Association), and the specific gravity of the resin solids is Approximate to 1.
また、上記水性塗料組成物は、酸化硬化を促進させるための触媒として金属ドライヤーを含有することもできる。かかる金属ドライヤーとしては、例えば、アルミニウム、カルシウム、セリウム、コバルト、鉄、リチウム、マグネシウム、マンガン、亜鉛、ジルコニウムよりなる群から選ばれる少なくとも１種の金属と酸との塩が挙げられ、該酸としては、例えば、カプリン酸、カプリル酸、イソデカン酸、リノレン酸、ナフテン酸、ネオデカン酸、オクテン酸、オレイン酸、パルミチン酸、樹脂酸、リシノール酸、大豆油脂肪酸、ステアリン酸、トール油脂肪酸等が挙げられる。 Moreover, the said water-based coating composition can also contain a metal dryer as a catalyst for promoting oxidative hardening. Examples of such metal dryers include salts of at least one metal selected from the group consisting of aluminum, calcium, cerium, cobalt, iron, lithium, magnesium, manganese, zinc, and zirconium with an acid. Examples include capric acid, caprylic acid, isodecanoic acid, linolenic acid, naphthenic acid, neodecanoic acid, octenoic acid, oleic acid, palmitic acid, resin acid, ricinoleic acid, soybean oil fatty acid, stearic acid, tall oil fatty acid and the like. It is done.
また、上記水性塗料組成物は、金属面などに直接塗布した場合に、該金属面の錆が塗膜表面にブリードして点錆などを発生させるのを抑制する効果があることから、亜硝酸塩、フィチン酸塩、タンニン酸塩、リン酸塩及びポリアミン化合物よりなる群から選ばれる少なくとも１種の化合物を含有することが望ましい。亜硝酸塩としては、例えば、亜硝酸ナトリウム、亜硝酸カルシウム、亜硝酸ストロンチウム、亜硝酸バリウム、亜硝酸アンモニウムなどが挙げられ、フィチン酸塩としては、例えば、フィチン酸ナトリウム、フィチン酸カリウムなどが挙げられ、タンニン酸塩としては、例えば、タンニン酸ナトリウム、タンニン酸カリウム等が挙げられ、ポリアミン化合物としては、例えば、Ｎ−（２−ヒドロキシエチル）エチレンジアミン三酢酸（ＨＥＤＴＡ）、エチレンジアミン四酢酸（ＥＤＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、プロピレンジアミン四酢酸（ＰＤＴＡ）、イミノ二酢酸、ニトリロ三酢酸（ＮＴＡ）、ジエチレントリアミンペンタメチレンホスホン酸（ＤＴＰＭＰ）、及びこれらのアルカリ金属塩；モノアルキルアミンやポリアミン、第四級アンモニウムイオンなどをトリポリリン酸二水素アルミニウムなどの層状りん酸塩にインターカレートしてなる層間化合物等が挙げられる。これらは単独でもしくは２種以上組み合わせて使用することができる。 In addition, the water-based coating composition has an effect of suppressing rust of the metal surface from bleeding to the surface of the coating film and generating spot rust when directly applied to a metal surface or the like. It is desirable to contain at least one compound selected from the group consisting of phytate, tannate, phosphate and polyamine compounds. Examples of the nitrite include sodium nitrite, calcium nitrite, strontium nitrite, barium nitrite, and ammonium nitrite.Examples of the phytate include sodium phytate and potassium phytate. Examples of the tannate include sodium tannate and potassium tannate. Examples of the polyamine compound include N- (2-hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), and diethylenetriamine. Pentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and alkali metal salts thereof; monoalkylamines and Riamin, intercalation compounds and the like formed by intercalating the like layered phosphate and quaternary ammonium ion such as dihydrogen tripolyphosphate aluminum. These can be used alone or in combination of two or more.
上記水性塗料組成物においては、上記成分の他に水溶性あるいはエマルション型のアルキド樹脂、シリコン樹脂、フッ素樹脂、エポキシ樹脂、ウレタン樹脂、ポリエステル樹脂、アミノ樹脂等の改質樹脂、イソシアネート化合物、ブロックイソシアネート化合物、メラミン等の硬化剤、顔料分散剤、界面活性剤、表面調整剤、可塑剤、沈降防止剤、帯電防止剤、抗菌剤、香料、紫外線吸収剤、紫外線安定剤、硬化触媒、分散剤、消泡剤、増粘剤、造膜助剤、防腐剤、防カビ剤、凍結防止剤、ｐＨ調整剤、フラッシュラスト抑止剤、アルデヒド捕捉剤、層状粘度鉱物、粉状もしくは微粒子状の活性炭、光触媒酸化チタン、アルキレングリコール変性アルキルシリケート等の低汚染化剤、等の添加剤を適宣選択し組み合わせて含有することができる。 In the aqueous coating composition, in addition to the above components, water-soluble or emulsion-type alkyd resins, silicone resins, fluororesins, epoxy resins, urethane resins, polyester resins, amino resins and other modified resins, isocyanate compounds, block isocyanates Compound, curing agent such as melamine, pigment dispersant, surfactant, surface conditioner, plasticizer, anti-settling agent, antistatic agent, antibacterial agent, fragrance, ultraviolet absorber, ultraviolet stabilizer, curing catalyst, dispersant, Antifoaming agent, thickener, film-forming aid, preservative, antifungal agent, antifreezing agent, pH adjuster, flash last inhibitor, aldehyde scavenger, layered viscosity mineral, powdered or fine particle activated carbon, photocatalyst Additives such as titanium dioxide and low-contaminants such as alkylene glycol-modified alkyl silicates can be selected and combined .
上記水性塗料組成物は、塗料固形分濃度が３０〜７０重量％、好ましくは４０〜６０重量％の範囲内になるように調整した後、１回あたりの塗付量が０．０５〜０．５Ｋｇ／ｍ２、好ましくは０．０８〜０．３Ｋｇ／ｍ２、さらに好ましくは０．１〜０．２Ｋｇ／ｍ２の範囲内となるようにして塗装することが望ましい。 The aqueous coating composition has a coating solid content concentration of 30 to 70% by weight, preferably 40 to 60% by weight, and the coating amount per time is 0.05 to 0.00. It is desirable to apply the coating so that it is within the range of 5 kg / m 2, preferably 0.08 to 0.3 kg / m 2, more preferably 0.1 to 0.2 kg / m 2.
塗装は、ローラー、エアスプレー、エアレススプレー、リシンガン、万能ガン、ハケ、静電塗装などの方法を用いて行うことができるが、高仕上がり性を得るためには、ローラー、エアスプレー、エアレススプレー、ハケによる等の方法で塗布することができ、また、乾燥方法としては、加熱乾燥、強制乾燥、常温乾燥のいずれであってもよい。本明細書では、４０℃未満の乾燥条件を常温乾燥とし、４０℃以上で且つ８０℃未満の乾燥条件を強制乾燥とし、８０℃以上の乾燥条件を加熱乾燥とする。 Painting can be done using methods such as roller, air spray, airless spray, lysine gun, universal gun, brush, electrostatic coating, etc., but in order to obtain high finish, roller, air spray, airless spray, It can be applied by a method such as brushing, and the drying method may be any of heat drying, forced drying, and room temperature drying. In the present specification, the drying condition of less than 40 ° C. is normal temperature drying, the drying condition of 40 ° C. or more and less than 80 ° C. is forced drying, and the drying condition of 80 ° C. or more is heat drying.
以下、実施例を挙げて本発明をさらに具体的に説明する。なお、「部」及び「％」は「重量部」及び「重量％」である。 Hereinafter, the present invention will be described more specifically with reference to examples. “Parts” and “%” are “parts by weight” and “% by weight”.
脂肪酸変性重合性不飽和モノマーの製造
製造例１
反応容器に下記の成分を入れ、攪拌しながら反応温度１４０℃で反応させ、脂肪酸変性重合性不飽和モノマー（ａ−１）を得た。エポキシ基とカルボキシル基の反応は残存カルボキシル基の量を測定することによりモニターした。反応が完了するまで約５時間を要した。
サフラワー油脂肪酸 ２８０部
グリシジルメタクリレート １４２部。
製造例２
反応させる成分を下記のものに変更する以外は製造例１と同様にして、脂肪酸変性重合性不飽和モノマー（ａ−２）を得た。
亜麻仁油脂肪酸 ２８０部
グリシジルメタクリレート １４２部。
Production of fatty acid-modified polymerizable unsaturated monomer Production Example 1
The following components were put into a reaction vessel and reacted at a reaction temperature of 140 ° C. with stirring to obtain a fatty acid-modified polymerizable unsaturated monomer (a-1). The reaction between epoxy groups and carboxyl groups was monitored by measuring the amount of residual carboxyl groups. It took about 5 hours to complete the reaction.
Safflower oil fatty acid 280 parts Glycidyl methacrylate 142 parts.
Production Example 2
A fatty acid-modified polymerizable unsaturated monomer (a-2) was obtained in the same manner as in Production Example 1 except that the components to be reacted were changed to the following.
Flaxseed oil fatty acid 280 parts Glycidyl methacrylate 142 parts.
水性脂肪酸変性樹脂分散体の製造
ガラスビーカーに下記成分を入れ、ディスパーにて２０００ｒｐｍで１５分間攪拌し、予備乳化液を製造した後、この予備乳化液を、高圧エネルギーを加えて流体同士を衝突させる高圧乳化装置にて１００ＭＰａで高圧処理することにより、分散粒子の平均粒子径が１９０ｎｍのモノマー乳化物を得た。
モノマー乳化物組成
脂肪酸変性重合性不飽和モノマー（ａ−１） ３０．１５部
スチレン １５部
２−ヒドロキシエチルメタクリレート ４．５部
ｉ―ブチルメタクリレート ２０．３５部
ｔ−ブチルメタクリレート ２０部
２−エチルヘキシルアクリレート ８部
メタクリル酸 ２部
ｎ−オクチル−３‐メルカプトプロピオネート ０．３部
「Ｎｅｗｃｏｌ７０７ＳＦ」(注１) １０部
脱イオン水 ８５部
次いで上記モノマー乳化物をフラスコへ移し、脱イオン水にて固形分濃度が４５％となるように希釈した。その後８５℃まで昇温させ、「ＶＡ−０８６」(注２)２部を脱イオン水１０部に溶解させた開始剤水溶液をフラスコに投入し、該温度を保持しながら３時間攪拌した。その後、「ＶＡ−０８６」(注２)０．５部を脱イオン水１０部に溶解させた開始剤水溶液をフラスコに添加し、該温度を保持しながら１時間攪拌した後４０℃まで冷却し、ジメチルアミノエタノールでｐＨを８．０に調整し、固形分濃度４０％、分散樹脂の平均粒子径が１８５ｎｍの水性樹脂分散体（Ｉ−１）を得た。
（注１）「Ｎｅｗｃｏｌ７０７ＳＦ」：商品名、日本乳化剤社製、ポリオキシエチレン鎖を有するアニオン性乳化剤、有効成分３０％、
（注２）「ＶＡ−０８６」：商品名、和光純薬社製、２，２’−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）−プロピオンアミド］。
製造例４〜５
モノマー乳化物の配合組成を表１に記載のとおりに変更する以外は上記製造例３と同様にして、水性脂肪酸変性樹脂分散体（Ｉ−２）〜（Ｉ−４）を得た。
Manufacture of aqueous fatty acid-modified resin dispersion The following components are put into a glass beaker and stirred at 2000 rpm for 15 minutes with a disper to prepare a pre-emulsified liquid. A monomer emulsion having an average particle size of the dispersed particles of 190 nm was obtained by high-pressure treatment at 100 MPa with a high-pressure emulsifier that collides each other.
Monomer emulsion composition Fatty acid-modified polymerizable unsaturated monomer (a-1) 30.15 parts Styrene 15 parts 2-hydroxyethyl methacrylate 4.5 parts i-butyl methacrylate 20.35 parts t-butyl methacrylate 20 parts 2-ethylhexyl acrylate 8 parts methacrylic acid 2 parts n-octyl-3-mercaptopropionate 0.3 part “Newcol 707SF” (Note 1) 10 parts deionized water 85 parts The above monomer emulsion is then transferred to a flask and deionized. Dilute with water to a solids concentration of 45%. Thereafter, the temperature was raised to 85 ° C., and an initiator aqueous solution in which 2 parts of “VA-086” (Note 2) was dissolved in 10 parts of deionized water was added to the flask, and stirred for 3 hours while maintaining the temperature. Thereafter, an initiator aqueous solution in which 0.5 part of “VA-086” (Note 2) was dissolved in 10 parts of deionized water was added to the flask, stirred for 1 hour while maintaining the temperature, and then cooled to 40 ° C. The pH was adjusted to 8.0 with dimethylaminoethanol to obtain an aqueous resin dispersion (I-1) having a solid content concentration of 40% and an average particle diameter of the dispersion resin of 185 nm.
(Note 1) “Newcol 707SF”: trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic emulsifier having a polyoxyethylene chain, 30% active ingredient,
(Note 2) “VA-086”: trade name, manufactured by Wako Pure Chemical Industries, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide].
Production Examples 4-5
Aqueous fatty acid-modified resin dispersions (I-2) to (I-4) were obtained in the same manner as in Production Example 3 except that the composition of the monomer emulsion was changed as shown in Table 1.
製造例７
脱イオン水３６部、「Ｎｅｗｃｏｌ７０７ＳＦ」０．３６部の入ったフラスコを、窒素置換後、８０℃まで加温した。内液を８０℃に維持しながら０．１部の過硫酸アンモニウムを加えてから下記組成の単量体エマルションを３時間にわたって滴下した。
Production Example 7
A flask containing 36 parts of deionized water and 0.36 part of “Newcol 707SF” was heated to 80 ° C. after purging with nitrogen. While maintaining the internal solution at 80 ° C., 0.1 part of ammonium persulfate was added, and then a monomer emulsion having the following composition was added dropwise over 3 hours.
脱イオン水 ５２．４部
スチレン １５部
ＭＭＡ ４０部
ｎ−ブチルアクリレート ４０部
メタクリル酸 ２部
ダイアセトンアクリルアミド ３部
「Ｎｅｗｃｏｌ７０７ＳＦ」 １０部
過硫酸アンモニウム ０．２部
滴下終了後３０分より、３０分間０．１部の過硫酸アンモニウムを1部の脱イオン水に溶かした溶液を滴下し、さらに２時間８０℃に保った。ジメチルアミノエタノールでｐＨを８．０に調整し、固形分濃度５０％、重量平均分子量１５万、ガラス転移温度２０．０℃の平均粒子径が１８５ｎｍの水性樹脂分散体（Ｉ−５）を得た。
Deionized water 52.4 parts Styrene 15 parts MMA 40 parts n-Butyl acrylate 40 parts Methacrylic acid 2 parts Diacetone acrylamide 3 parts "Newcol 707SF" 10 parts Ammonium persulfate 0.2 parts 30 minutes after completion of dropping, 30 minutes 0. A solution of 1 part ammonium persulfate in 1 part deionized water was added dropwise and kept at 80 ° C. for an additional 2 hours. The pH was adjusted to 8.0 with dimethylaminoethanol to obtain an aqueous resin dispersion (I-5) having a solid content concentration of 50%, a weight average molecular weight of 150,000, a glass transition temperature of 20.0 ° C. and an average particle diameter of 185 nm. It was.
製造例８
脱イオン水３６部、「Ｎｅｗｃｏｌ７０７ＳＦ」０．３６部の入ったフラスコを、窒素置換後、８０℃まで加温した。内液を８０℃に維持しながら０．１部の過硫酸アンモニウムを加えてから下記組成の単量体エマルションを３時間にわたって滴下した。
Production Example 8
A flask containing 36 parts of deionized water and 0.36 part of “Newcol 707SF” was heated to 80 ° C. after purging with nitrogen. While maintaining the internal solution at 80 ° C., 0.1 part of ammonium persulfate was added, and then a monomer emulsion having the following composition was added dropwise over 3 hours.
脱イオン水 ５２．４部
スチレン １８部
ＭＭＡ ４０部
ｎ−ブチルアクリレート ４０部
メタクリル酸 ２部
「Ｎｅｗｃｏｌ７０７ＳＦ」 １０部
過硫酸アンモニウム ０．２部
滴下終了後３０分より、３０分間０．１部の過硫酸アンモニウムを1部の脱イオン水に溶かした溶液を滴下し、さらに２時間８０℃に保った。ジメチルアミノエタノールでｐＨを８．０に調整し、固形分濃度５０％、重量平均分子量１５万、ガラス転移温度２０．５℃の平均粒子径が１８５ｎｍの水性樹脂分散体（Ｉ−６）を得た。
Deionized water 52.4 parts Styrene 18 parts MMA 40 parts n-Butyl acrylate 40 parts Methacrylic acid 2 parts "Newcol 707SF" 10 parts Ammonium persulfate 0.2 parts From 30 minutes after completion of dropping, 0.1 part ammonium persulfate for 30 minutes Was added dropwise in 1 part of deionized water and kept at 80 ° C. for 2 hours. The pH was adjusted to 8.0 with dimethylaminoethanol to obtain an aqueous resin dispersion (I-6) having a solid content concentration of 50%, a weight average molecular weight of 150,000, a glass transition temperature of 20.5 ° C. and an average particle diameter of 185 nm. It was.
水性塗料組成物の製造
実施例１〜４及び比較例１〜３
容器に表２に記載の組成（Ａ）に示される各成分を順次仕込み、ディスパーで３０分間均一になるまで攪拌を続け、各顔料ペーストを得た。その後、該各顔料ペーストに表２記載の各水性樹脂分散体を仕込み、さらに表２に記載の組成（Ｂ）に示す各成分を順次添加し、各水性塗料組成物を得た。ついで、各水性塗料組成物を下記基準にて評価した。結果を表２に示す。
Production Examples 1-4 and Comparative Examples 1-3 of aqueous coating compositions
Each component shown in the composition (A) shown in Table 2 was sequentially charged into a container, and stirring was continued with a disper for 30 minutes until it became uniform to obtain each pigment paste. Thereafter, each aqueous resin dispersion described in Table 2 was charged into each pigment paste, and further each component shown in the composition (B) described in Table 2 was added in order to obtain each aqueous coating composition. Subsequently, each water-based coating composition was evaluated according to the following criteria. The results are shown in Table 2.
（注３）「スラオフ７２Ｎ」：商品名、武田薬品工業（株）製、防腐剤
（注４）「ノプコサントＫ」：商品名、サンノプコ社製、顔料分散剤
（注５）「アデカノールＵＨ−４３８」：商品名、アデカ社製、増粘剤
（注６）「チタン白ＪＲ−６００Ａ」：商品名、テイカ社製、チタン白、比重４．１
（注７）「ＳＮデフォーマー３８０」：商品名、サンノプコ社製、消泡剤
（注８）「ＤＩＣＮＡＴＥ１０００Ｗ」：商品名、大日本インキ社製、金属ドライヤー、Ｃｏ含有率３．６％
（注９）「ＴＥＸＡＮＯＬ」：商品名、イーストマンケミカル社製、２，２，４−トリメチルー１，３−ペンタンジオールモノイソブチレート、造膜助剤。
(Note 3) “Suraoff 72N”: trade name, manufactured by Takeda Pharmaceutical Co., Ltd., preservative (Note 4) “Nopco Santo K”: trade name, manufactured by San Nopco, pigment dispersant (Note 5) “Adecanol UH-438 ": Brand name, manufactured by Adeka Corporation, thickener (Note 6)" Titanium white JR-600A ": Brand name, manufactured by Teika Corporation, titanium white, specific gravity 4.1
(Note 7) “SN Deformer 380”: trade name, manufactured by San Nopco, defoaming agent (Note 8) “DICnate 1000W”: trade name, manufactured by Dainippon Ink, metal dryer, Co content 3.6%
(Note 9) “TEXANOL”: trade name, manufactured by Eastman Chemical Co., Ltd., 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, film-forming aid.
（＊１）硬化性
各水性塗料組成物を離型紙に膜厚が２０μｍになるように塗布し、１週間乾燥させた後、遊離塗膜を２０℃のアセトン溶剤に入れ、２４時間抽出した後の塗膜の残存率（％）を調べた。値が高い程硬化性が良好であることを示す。
（＊２）肉持ち感
各水性塗料組成物を６ミルドクターブレードを用いてガラス板に塗装し、気温２０℃、相対湿度６０％の条件下で乾燥させて各試験塗板を得た。１日後に塗膜外観を目視にて評価した。
○： 肉持ち感に優れる。
△： 肉持ち感に乏しい。
（＊３）光沢
上記（２）と同様にして得た試験塗板の６０度グロスを測定した。値が大きい程光沢が良好であることを示す。
（＊４）耐水性
ＪＩＳ Ｋ ５４１０に規定する鋼板（１５０×７０×０．８ｍｍ）をキシレンにて脱脂し、その上に、各水性塗料組成物を上水で約７０ＫＵに希釈して刷毛にて塗布量が１５０ｇ／ｍ２となるようにして塗装し、気温２０℃、相対湿度６０％の条件下で１週間乾燥させて各試験塗板を得た。各試験塗板を、ＪＩＳ Ｋ ５４００の８．１９に準じて耐水性試験（９６時間浸漬）に供した。試験後の各塗面を下記基準で評価した。
○：割れ、はがれがなく、また光沢保持率が７０％以上である。
×：上記の内、１つでも該当しないものがある。
（＊５）初期耐水性
ＪＩＳ Ｋ ５４１０に規定する鋼板（１５０×７０×０．８ｍｍ）をキシレンにて脱脂し、その上に、各水性塗料組成物を上水で約７０ＫＵに希釈して刷毛にて塗布量が１５０ｇ／ｍ２となるようにして塗装し、気温２０℃、相対湿度６０％の条件下で１時間乾燥させ各試験塗板を得た。各試験板を１０分間没水して塗膜外観を目視評価した。
○：ややツヤビケまたはフクレが見られるものの実用上問題ない。
△：フクレが大きいか多数見られるまたは一部塗膜溶出が見られる。
×：塗膜溶出が著しい
（＊６）防食性
素材としてＪＩＳ Ｋ ５４１０に規定する鋼板（１５０×７０×０．８ｍｍ）をキシレンにて脱脂したものを使用し、これに各水性塗料組成物を上水で約７０ＫＵに希釈し、刷毛にて塗付量１００ｇ／ｍ２となるようにして塗装した。
さらに乾燥１日後に２回目の塗装を１回目と同様に行ない、気温２０℃、相対湿度６０％の条件下で７日乾燥させて各試験塗板を作成した。各試験塗板をＪＩＳ Ｋ ５６２１に規定されている耐複合サイクル防食性試験に３６サイクル供して、その塗膜面を下記基準で評価した。
○：塗膜にさびが認められない、
△：塗膜に一部さびが認められる、
×：塗膜の全面にさびが認められる。
（＊７）促進耐候性
防食性試験用と同様に作成した各試験塗板を、ＪＩＳ Ｋ ５４００の９．８．１（サンシャインカーボンアーク灯式）の促進耐候性試験に準じて、１０００時間照射した後、各塗板面をＪＩＳ Ｋ ５４００の９．６白亜化度によって評価した。点数が低いほど白亜化が進んでいることを示す。
（＊８）ホルムアルデヒド吸着除去性
コニカルビーカーに、防食性試験用と同様に作成した試験板を吊るした後、ホルムアルデヒドが４０ｐｐｍの濃度で発生するように、所定量のホルムアルデヒド水溶液を加えた。シーロンフィルムにて密閉した後、室温にて２４時間放置した。ガス検知管により、２４時間後におけるホルムアルデヒドの残留濃度を測定し、そのホルムアルデヒド吸着除去性を下記基準で評価した。
○：２ｐｐｍ未満
△：２ｐｐｍ以上
(* 1) After each curable aqueous coating composition was applied to a release paper to a film thickness of 20 μm and dried for 1 week, the free coating film was placed in an acetone solvent at 20 ° C. and extracted for 24 hours. The remaining rate (%) of the coating film was examined. Higher values indicate better curability.
(* 2) Feeling of meat Each water-based paint composition was applied to a glass plate using a 6 mil doctor blade, and dried under conditions of an air temperature of 20 ° C. and a relative humidity of 60% to obtain test coating plates. The appearance of the coating film was visually evaluated after 1 day.
○: Excellent meat feeling.
Δ: Poor feeling of meat
(* 3) Gloss 60 degree gloss of the test coated plate obtained in the same manner as in (2) above was measured. The larger the value, the better the gloss.
(* 4) Water resistance The steel plate (150 × 70 × 0.8 mm) specified in JIS K 5410 is degreased with xylene, and then each aqueous coating composition is diluted to about 70 KU with clean water to make a brush. The coating amount was 150 g / m 2 and the coating was dried for one week under conditions of an air temperature of 20 ° C. and a relative humidity of 60% to obtain each test coated plate. Each test coated plate was subjected to a water resistance test (96 hours immersion) according to JIS K 5400 8.19. Each coated surface after the test was evaluated according to the following criteria.
○: There is no cracking or peeling, and the gloss retention is 70% or more.
×: Among the above, there is one that does not correspond.
(* 5) Initial water resistance A steel plate (150 × 70 × 0.8 mm) specified in JIS K 5410 is degreased with xylene, and each water-based coating composition is diluted to about 70 KU with clean water and then brushed. The coating amount was 150 g / m 2 and dried for 1 hour under conditions of an air temperature of 20 ° C. and a relative humidity of 60% to obtain each test coated plate. Each test plate was submerged for 10 minutes, and the appearance of the coating film was visually evaluated.
○: Slight shine or swelling is observed but there is no practical problem.
(Triangle | delta): A bulge is large or many are seen, or one part coating film elution is seen.
×: Elution of the coating film is remarkable (* 6) A steel plate (150 × 70 × 0.8 mm) defined in JIS K 5410 is used as an anticorrosive material and degreased with xylene. The mixture was diluted to about 70 KU with clean water and applied with a brush so that the application amount was 100 g / m2.
Further, after the first drying, the second coating was performed in the same manner as the first coating, and each test coating plate was prepared by drying for 7 days under the conditions of an air temperature of 20 ° C. and a relative humidity of 60%. Each test coating plate was subjected to 36 cycles of a combined cycle anti-corrosion resistance test specified in JIS K 5621, and the coating surface was evaluated according to the following criteria.
○: Rust is not recognized in the coating film,
Δ: Some rust is observed in the coating film,
X: Rust is recognized on the entire surface of the coating film.
(* 7) Each test coated plate prepared in the same manner as for the accelerated weather resistance and corrosion resistance test was irradiated for 1000 hours in accordance with the accelerated weather resistance test of 9.8.1 (Sunshine carbon arc lamp type) of JIS K 5400. Then, each coated plate surface was evaluated by 9.6 chalking degree of JIS K 5400. The lower the score, the more chalking is progressing.
(* 8) Formaldehyde adsorption removability After hanging a test plate prepared in the same manner as in the anticorrosion test on a conical beaker, a predetermined amount of an aqueous formaldehyde solution was added so that formaldehyde was generated at a concentration of 40 ppm. After sealing with a Ceylon film, it was left at room temperature for 24 hours. The residual concentration of formaldehyde after 24 hours was measured with a gas detector tube, and the formaldehyde adsorption removal property was evaluated according to the following criteria.
○: Less than 2 ppm Δ: 2 ppm or more
Claims (7)
その他の重合性不飽和モノマー（ｂ）が、酸基含有重合性不飽和モノマー（ｂ１）と、炭素数が４以上の直鎖状、分岐状もしくは環状で飽和又は不飽和の炭化水素基を含有する重合性不飽和モノマー（ｂ２）と、ならびに他の重合性不飽和モノマー（ｂ７）とを含んでなり、他の重合性不飽和モノマー（ｂ７）が、モノマー（ａ）、モノマー（ｂ１）及びモノマー（ｂ２）以外の重合性不飽和モノマーであって、
モノマー（ａ）及びモノマー（ｂ）の合計重量に基づいて、モノマー（ａ）を５〜５０重量％、モノマー（ｂ１）を０．１〜５重量％、モノマー（ｂ２）を４５〜８０重量％及び他の重合性不飽和モノマー（ｂ７）を０〜４９．９重量％含有し、ここで炭素数４以上の炭化水素基を含有する重合性不飽和モノマー（ｂ２）が、炭素数６以上の直鎖状もしくは分岐状の炭化水素基を有する重合性不飽和モノマー（ｂ３）を、モノマー（ａ）及びモノマー（ｂ）の合計重量に基づいて、１〜３０重量％の範囲内で含んでなる
モノマー混合物を水性媒体中に平均粒子径が５００ｎｍ以下になるように微分散させ、得られる乳化物を重合することにより製造される水性脂肪酸変性樹脂分散体、（Ｂ）分散体（Ａ）以外であって、ヒドラジン誘導体（Ｃ）と架橋反応可能なカルボニル基を含有する水性樹脂分散体ならびに（Ｃ）ヒドラジン誘導体を含有し、樹脂（Ａ）と樹脂（Ｂ）の配合比が、固形分重量比で１０／９０〜９０／１０の範囲内、ヒドラジン誘導体（Ｃ）の配合量が樹脂（Ａ）及び樹脂（Ｂ）の合計の樹脂固形分を基準にして、０．０１〜１０重量％にある硬化型水性樹脂組成物。 (A) Other than fatty acid-modified polymerizable unsaturated monomer (a) and fatty acid-modified polymerizable unsaturated monomer (a) obtained by reacting fatty acid (a1) with epoxy group-containing polymerizable unsaturated monomer (a2) A polymerizable unsaturated monomer (b)
The other polymerizable unsaturated monomer (b) contains an acid group-containing polymerizable unsaturated monomer (b1) and a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 4 or more carbon atoms. A polymerizable unsaturated monomer (b2), and other polymerizable unsaturated monomer (b7), wherein the other polymerizable unsaturated monomer (b7) comprises monomer (a), monomer (b1) and A polymerizable unsaturated monomer other than the monomer (b2),
Based on the total weight of monomer (a) and monomer (b), monomer (a) is 5 to 50% by weight, monomer (b1) is 0.1 to 5% by weight, and monomer (b2) is 45 to 80% by weight. And 0 to 49.9% by weight of other polymerizable unsaturated monomer (b7), wherein the polymerizable unsaturated monomer (b2) containing a hydrocarbon group having 4 or more carbon atoms is 6 or more carbon atoms. The polymerizable unsaturated monomer (b3) having a linear or branched hydrocarbon group is included in the range of 1 to 30% by weight based on the total weight of the monomer (a) and the monomer (b). An aqueous fatty acid-modified resin dispersion produced by finely dispersing a monomer mixture in an aqueous medium so that the average particle size is 500 nm or less and polymerizing the resulting emulsion, (B) dispersion ( be other than a), a hydrazine derivative It contains an aqueous resin dispersion and (C) hydrazine derivative containing C) and crosslinkable group, compounding ratio of the resin (A) and the resin (B), by solids weight ratio 10 / 90-90 / 10, within a range of 0.01 to 10% by weight, based on the total resin solid content of the resin (A) and the resin (B), the hydrazine derivative (C) content is curable aqueous resin composition .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004189214A JP4673010B2 (en) | 2004-06-28 | 2004-06-28 | Curable water-based resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004189214A JP4673010B2 (en) | 2004-06-28 | 2004-06-28 | Curable water-based resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006008876A JP2006008876A (en) | 2006-01-12 |
| JP4673010B2 true JP4673010B2 (en) | 2011-04-20 |
Family
ID=35776475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004189214A Expired - Fee Related JP4673010B2 (en) | 2004-06-28 | 2004-06-28 | Curable water-based resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4673010B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4559152B2 (en) * | 2004-07-30 | 2010-10-06 | 関西ペイント株式会社 | Aqueous resin composition |
| JP5043391B2 (en) * | 2006-09-21 | 2012-10-10 | 関西ペイント株式会社 | Curable water-based resin composition |
| JP5026811B2 (en) * | 2006-11-06 | 2012-09-19 | エスケー化研株式会社 | Painting method |
| JP2008248155A (en) * | 2007-03-30 | 2008-10-16 | Dic Corp | Aqueous one-component coating agent and coated article |
| JP5451025B2 (en) * | 2008-10-10 | 2014-03-26 | 関西ペイント株式会社 | One-component water-based paint composition for construction machinery or industrial machinery |
| JP6972726B2 (en) * | 2017-07-20 | 2021-11-24 | 藤倉化成株式会社 | Multicolored paint composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5628251A (en) * | 1979-08-17 | 1981-03-19 | Kansai Paint Co Ltd | Water-based coating composition |
| JPS6164329A (en) * | 1984-09-07 | 1986-04-02 | Showa Highpolymer Co Ltd | Preparation of oxidation curable type aqueous emulsion |
| JPH05222296A (en) * | 1992-02-14 | 1993-08-31 | Mitsubishi Yuka Badische Co Ltd | Water-based cross-linking resin composition |
| JP3895827B2 (en) * | 1997-05-26 | 2007-03-22 | 関西ペイント株式会社 | Copolymer aqueous dispersion and resin composition for water-based paint containing the same |
-
2004
- 2004-06-28 JP JP2004189214A patent/JP4673010B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006008876A (en) | 2006-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5016817B2 (en) | Method for producing aqueous resin dispersion | |
| JP5512981B2 (en) | Water-based paint composition and coating method using the composition | |
| JP4674067B2 (en) | Modified starch-containing resin aqueous dispersion and method for producing the aqueous dispersion | |
| JP2008001779A (en) | Aqueous resin composition, aqueous coating composition, and method for forming coated film by using the same | |
| JP2007291157A (en) | Aqueous resin composition and paint composition containing the same | |
| JP5043391B2 (en) | Curable water-based resin composition | |
| JP2006056973A (en) | Method for producing aqueous resin dispersion | |
| JP4559152B2 (en) | Aqueous resin composition | |
| JP2006052283A (en) | Method for producing aqueous dispersion of organopolysiloxane | |
| JP4673010B2 (en) | Curable water-based resin composition | |
| JP2007297491A (en) | Curable aqueous resin composition | |
| JP4411108B2 (en) | Paint finishing method | |
| JP4791003B2 (en) | Biodegradable resin-containing aqueous dispersion and method for producing the aqueous dispersion | |
| JP4410624B2 (en) | Method for producing silicon-containing resin aqueous dispersion | |
| JP4948047B2 (en) | Oxidative curing paint | |
| JP4410623B2 (en) | Method for producing aqueous resin dispersion | |
| JP4608259B2 (en) | Aqueous resin composition | |
| JP5348729B2 (en) | Method for producing aqueous resin dispersion | |
| JP2005343966A (en) | Manufacturing method of aqueous resin dispersion | |
| JP5635798B2 (en) | Emulsion resin paint | |
| JP4456409B2 (en) | Method for producing aqueous fatty acid-modified epoxy resin dispersion | |
| JP5865250B2 (en) | Aqueous epoxy resin coating composition kit, aqueous epoxy resin coating composition, method for forming coated article, and coated article | |
| JP4908949B2 (en) | Fatty acid-modified resin water dispersion and production method | |
| JP2006052310A (en) | Method for producing polysiloxane composite polymer particle | |
| JP2006045452A (en) | Curable water-base resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070531 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20091028 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100216 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100416 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101005 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101203 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110118 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110120 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4673010 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140128 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140128 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |