JP4451216B2 - Water based sealer - Google Patents
Water based sealer Download PDFInfo
- Publication number
- JP4451216B2 JP4451216B2 JP2004162089A JP2004162089A JP4451216B2 JP 4451216 B2 JP4451216 B2 JP 4451216B2 JP 2004162089 A JP2004162089 A JP 2004162089A JP 2004162089 A JP2004162089 A JP 2004162089A JP 4451216 B2 JP4451216 B2 JP 4451216B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- mol
- aqueous
- structural unit
- polycarboxylic acid
- 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 - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 53
- 229920000642 polymer Polymers 0.000 claims description 90
- 239000000178 monomer Substances 0.000 claims description 65
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 52
- 239000002253 acid Substances 0.000 claims description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 238000006386 neutralization reaction Methods 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229920006317 cationic polymer Polymers 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 25
- 230000003472 neutralizing effect Effects 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 238000005470 impregnation Methods 0.000 description 15
- 239000000049 pigment Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 239000004566 building material Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000007774 longterm Effects 0.000 description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 239000007870 radical polymerization initiator Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- -1 For example Inorganic materials 0.000 description 7
- 239000004567 concrete Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- 239000010454 slate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 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 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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- IMWCPTKSESEZCL-AHUNZLEGSA-H (Z)-but-2-enedioate iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O IMWCPTKSESEZCL-AHUNZLEGSA-H 0.000 description 1
- IMWCPTKSESEZCL-SPSNFJOYSA-H (e)-but-2-enedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)\C=C\C([O-])=O.[O-]C(=O)\C=C\C([O-])=O.[O-]C(=O)\C=C\C([O-])=O IMWCPTKSESEZCL-SPSNFJOYSA-H 0.000 description 1
- SHVRRGGZMBWAJT-ODZAUARKSA-N (z)-but-2-enedioic acid;copper Chemical compound [Cu].OC(=O)\C=C/C(O)=O SHVRRGGZMBWAJT-ODZAUARKSA-N 0.000 description 1
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- AAMTXHVZOHPPQR-UHFFFAOYSA-N 2-(hydroxymethyl)prop-2-enoic acid Chemical compound OCC(=C)C(O)=O AAMTXHVZOHPPQR-UHFFFAOYSA-N 0.000 description 1
- ZEYKLMDPUOVUCR-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC=C(Cl)C(S(Cl)(=O)=O)=C1 ZEYKLMDPUOVUCR-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
- FERWBXLFSBWTDE-UHFFFAOYSA-N 3-aminobutan-2-ol Chemical compound CC(N)C(C)O FERWBXLFSBWTDE-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000233967 Anethum sowa Species 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- VUCAVCCCXQVHAN-UHFFFAOYSA-L azane dichlorocopper Chemical compound N.Cl[Cu]Cl VUCAVCCCXQVHAN-UHFFFAOYSA-L 0.000 description 1
- GLMQHZPGHAPYIO-UHFFFAOYSA-L azanium;2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [NH4+].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O GLMQHZPGHAPYIO-UHFFFAOYSA-L 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- KZBRSTGECTWPFL-UHFFFAOYSA-N copper;acetyl acetate Chemical compound [Cu+2].CC(=O)OC(C)=O KZBRSTGECTWPFL-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000001514 detection method Methods 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
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000004225 ferrous lactate Substances 0.000 description 1
- 235000013925 ferrous lactate Nutrition 0.000 description 1
- 229940037907 ferrous lactate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229960002598 fumaric acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical compound C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GJYMQFMQRRNLCY-UHFFFAOYSA-N pent-3-en-2-ol Chemical group CC=CC(C)O GJYMQFMQRRNLCY-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 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
- 239000002244 precipitate Substances 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical group OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、ポリカルボン酸系重合体を用いた水性シーラーに関する。 The present invention relates to an aqueous sealer using a polycarboxylic acid polymer.
カルボキシル基を含有するポリカルボン酸系重合体は、その水溶解性を利用して、従来から各種用途に用いられている。例えば、洗剤ビルダー、スケール防止剤、キレート剤、セメント減水剤、インキ用バインダー、フィルム成形品、パルプ成形品、シート成形品、ラミネート用材料、例えば、車両用、プラスチック成形品用、家電品用、鋼製品、大型構造物、航空機用、建材用、建築用、瓦用、木工用などの上塗りもしくは中塗り水性塗料や水性シーラー等に有用であることが知られている。
なかでも、上記ポリカルボン酸系重合体を、コンクリートや無機質建材等の多孔質の材料に対して長期の耐水性を発揮させるための、樹脂溶液型の水性シーラーに用いた場合、樹脂エマルション型の水性シーラー（例えば、特許文献１参照。）に比べて、上記多孔質部分に良好に浸透させることができるため、優れた密着性（含浸密着性）や長期の耐水性等を発揮することができ有用である上、その需要も大きい。
In particular, when the polycarboxylic acid polymer is used in a resin solution type aqueous sealer for exhibiting long-term water resistance against porous materials such as concrete and inorganic building materials, the resin emulsion type Compared to an aqueous sealer (for example, see Patent Document 1), the porous portion can be permeated well, so that excellent adhesion (impregnation adhesion), long-term water resistance, etc. can be exhibited. In addition to being useful, the demand is also great.
しかしながら、従来の、ポリカルボン酸系重合体を用いた樹脂溶液型の水性シーラーでは、その含浸密着性は、樹脂エマルション型のものに比べ優れているもののまだ十分とは言えず、近年の使用用途の拡大等とも相まって、さらに高い含浸密着性を発揮し得るものが求められている。また、上記樹脂溶液型の水性シーラーでは、その樹脂成分はもともと水溶性であるため、長期間にわたり何度も水が接触すると、一旦形成した塗膜部分において樹脂が再溶出したり剥がれ落ちたりしやすく、長期間良好な耐水性を発揮することが困難であった。
そこで、本発明が解決しようとする課題は、例えば、基材に対する含浸密着性に優れ、かつ、長期間良好な耐水性を発揮する水性シーラーを提供することにある。
However, in the conventional resin solution type aqueous sealer using a polycarboxylic acid polymer, the impregnation adhesion is superior to that of the resin emulsion type, but it is still not sufficient. In combination with the expansion of the above, there is a demand for a material that can exhibit even higher impregnation adhesion. Moreover, in the resin solution type aqueous sealer, the resin component is originally water-soluble, and therefore when the resin is contacted many times over a long period of time, the resin may be re-eluted or peeled off at the coating film once formed. It was easy to achieve good water resistance for a long time.
Therefore, an object of the present invention is to provide, for example, excellent in impregnation adhesion to the substrate, and to provide an aqueous sealer over which exhibits good water resistance long term.
本発明者は、上記課題を解決するべく鋭意検討を行った。その結果、ポリカルボン酸系重合体の構成要素であるカルボキシル基含有不飽和単量体に由来する構成単位全体のうちの、特定の割合分において、カルボキシル基が多価金属で中和された状態となっているポリカルボン酸系重合体を用いる水性シーラーであれば、上記課題を一挙に解決できることを見出した。詳しくは、基材表面に塗布する段階までは、水溶性を保持しておく必要があるが、その反面、塗膜の形成後は、この水溶性のために、樹脂成分が再溶出したり剥がれやすくなり、長期間にわたって優れた耐水性を発揮することは困難であったところ、本発明者は、ポリカルボン酸系重合体のカルボキシル基を特定の割合で中和しておくことにより、塗布段階においては、一部不溶化（疎水化）していても全体としては水溶性を保持している状態にし、塗膜の形成後はコンクリートや無機質建材等の基材側から供給されるカルシウムイオン等により全体としても水溶性を保持し得ない程度に実質的に完全に不溶化させるようにすれば良いこと、すなわち、初期中和率が調整されたポリカルボン酸系重合体を用いればよいことを見出したのである。
上記中和を特定の多価金属で行うようにすると、前述した適度な不溶化の度合いが良好に制御できるとともに、強度（硬度）の高い重合体となり、一旦基材に含浸した重合体が強固に固定されることになり、非常に優れた密着性（含浸密着性）を発揮するものとなる上、塗膜全体としても強度に優れたものとなる。
The present inventor has intensively studied to solve the above problems. As a result, the carboxyl group is neutralized with a polyvalent metal in a specific proportion of the entire structural unit derived from the carboxyl group-containing unsaturated monomer that is a component of the polycarboxylic acid polymer. It has been found that the above-described problems can be solved at once by using an aqueous sealer using a polycarboxylic acid polymer. Specifically, it is necessary to maintain water solubility until the stage of application to the surface of the substrate, but on the other hand, after the formation of the coating film, the resin component is re-eluted or peeled off due to this water solubility. It was difficult to exert excellent water resistance over a long period of time, and the present inventor made the application step by neutralizing the carboxyl group of the polycarboxylic acid polymer at a specific ratio. In this case, even if it is partially insolubilized (hydrophobized), it remains water-soluble as a whole, and after formation of the coating film, it is caused by calcium ions supplied from the base material side of concrete, inorganic building materials, etc. It has been found that it is only necessary to insolubilize substantially completely to the extent that water solubility cannot be maintained as a whole , that is , a polycarboxylic acid polymer with an adjusted initial neutralization rate may be used. Is
When to perform the above SL neutralized with certain multivalent metal, with the degree of moderate insolubilization described above can be satisfactorily controlled, the intensity becomes a polymer having a high (hardness), once firmly polymer impregnated into the substrate In addition to exhibiting excellent adhesion (impregnation adhesion), the coating film as a whole has excellent strength.
以上の知見により、本発明は完成された。
したがって、本発明にかかる水性シーラーは、ポリカルボン酸系重合体と水とを含み、前記ポリカルボン酸系重合体がモノエチレン性のカルボキシル基含有不飽和単量体に由来する構成単位を必須としてなり、かつ、前記構成単位が有する全カルボキシル基のうちの１モル％以上が多価金属で中和されてなる、水性シーラーである。
Based on the above findings, the present invention has been completed.
Thus, aqueous sealer according to the present invention, viewed contains a port polycarboxylic acid polymer and water, a constituent unit wherein the polycarboxylic acid polymer is derived from a monoethylenically unsaturated monomer containing a carboxyl group Required And an aqueous sealer in which 1 mol% or more of all the carboxyl groups of the structural unit is neutralized with a polyvalent metal .
本発明によれば、基材に対する含浸密着性に優れ、かつ、長期間良好な耐水性を発揮する水性シーラーを提供することができる。 According to the present invention, excellent in impregnation adhesion to substrates, and can provide an aqueous sealer over which exhibits good water resistance long term.
以下、本発明にかかる水性シーラーおよびそれを得るためのポリカルボン酸系重合体（以下、本発明にかかるポリカルボン酸系重合体と称することがある。）について詳しく説明するが、本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更実施し得る。
〔ポリカルボン酸系重合体〕
本発明にかかるポリカルボン酸系重合体（以下、本発明の重合体と称することがある。）は、前述したように、カルボキシル基含有不飽和単量体に由来する構成単位を必須としてなる重合体である。
上記カルボキシル基含有不飽和単量体としては、限定はされないが、例えば、アクリル酸、メタクリル酸、クロトン酸、α−ヒドロキシアクリル酸等のモノカルボン酸モノエチレン性不飽和単量体；マレイン酸、フマル酸、シトラコン酸、アコニット酸、イタコン酸等のジカルボン酸モノエチレン性不飽和単量体；等が好ましく挙げられ、なかでも、（共）重合性が良好であり、分子量制御が容易である点で、モノカルボン酸モノエチレン性不飽和単量体がより好ましく、さらに好ましくはアクリル酸およびメタクリル酸、特に好ましくはアクリル酸である。
Hereinafter, the present invention written that water sealers and it obtained for polycarboxylic acid polymer (hereinafter sometimes referred to as such polycarboxylic acid polymer in the present invention.) Although described in detail. The present The scope of the invention is not limited to these descriptions, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention.
[Polycarboxylic acid polymer]
As described above, the polycarboxylic acid-based polymer according to the present invention (hereinafter sometimes referred to as the polymer of the present invention) has a structural unit derived from a carboxyl group-containing unsaturated monomer as an essential component. It is a coalescence.
Examples of the carboxyl group-containing unsaturated monomer include, but are not limited to, monocarboxylic acid monoethylenically unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, and α-hydroxyacrylic acid; maleic acid, Preferred examples include dicarboxylic acid monoethylenically unsaturated monomers such as fumaric acid, citraconic acid, aconitic acid, and itaconic acid. Among them, (co) polymerizability is good, and molecular weight control is easy. In particular, monoethylenically unsaturated monocarboxylic acid monomers are more preferable, acrylic acid and methacrylic acid are more preferable, and acrylic acid is particularly preferable.
本発明の重合体中、上記カルボキシル基含有不飽和単量体由来の構成単位の含有割合は、限定はされないが、本発明の重合体を構成している単量体由来の構成単位全体に対し、３０モル％以上であることが好ましく、より好ましくは５０モル％以上、さらに好ましくは７０モル％以上であり、特に好ましくは１００モル％である。上記含有割合が３０モル％未満であると、そのほかの共重合組成にもよるが、水溶性を保てなくなるおそれがある。
本発明の重合体においては、単量体由来の構成単位として、上記カルボキシル基含有不飽和単量体以外の他の単量体に由来する構成単位を、本発明の効果が損なわれない範囲内で、適宜含有していてもよい。
In the polymer of the present invention, the content ratio of the structural unit derived from the carboxyl group-containing unsaturated monomer is not limited, but with respect to the entire structural unit derived from the monomer constituting the polymer of the present invention. , 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, and particularly preferably 100 mol%. If the content is less than 30 mol%, it may depend on the other copolymer composition, but water solubility may not be maintained.
In the polymer of the present invention, as a monomer-derived structural unit, a structural unit derived from a monomer other than the carboxyl group-containing unsaturated monomer is within the range where the effects of the present invention are not impaired. And you may contain suitably.
上記他の単量体としては、上記カルボキシル基含有不飽和単量体と共重合可能な単量体であればよく、限定はされないが、水溶性の単量体が好ましく、例えば、ビニルスルホン酸、アリルスルホン酸および３−アリロキシ−２−ヒドロキシプロパンスルホン酸等のスルホン酸基を含有するモノエチレン性不飽和単量体ならびに該不飽和単量体を部分中和または完全中和した塩；３−メチル−２−ブテン−１−オール（プレノール）、３−メチル−３−ブテン−１−オール（イソプレノール）、２−ヒドロキシアクリレートおよび２−ヒドロキシメチルアクリレート等の水酸基を含有する不飽和単量体；などが好ましく挙げられ、なかでも、スルホン酸基を含有するモノエチレン性不飽和単量体および該不飽和単量体を部分中和または完全中和した塩がより好ましい。 The other monomer may be any monomer that can be copolymerized with the carboxyl group-containing unsaturated monomer, and is not limited, but is preferably a water-soluble monomer such as vinyl sulfonic acid. Monoethylenically unsaturated monomers containing sulfonic acid groups such as allylsulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid, and salts obtained by partially neutralizing or completely neutralizing the unsaturated monomer; 3 -Unsaturated monomers containing hydroxyl groups such as methyl-2-buten-1-ol (prenol), 3-methyl-3-buten-1-ol (isoprenol), 2-hydroxyacrylate and 2-hydroxymethylacrylate Among them, a monoethylenically unsaturated monomer containing a sulfonic acid group and partial or complete neutralization of the unsaturated monomer are preferable. Salt is more preferable.
本発明の重合体においては、必須構成単位であるカルボキシル基含有不飽和単量体由来の構成単位が有する全カルボキシル基のうちの１モル％以上が多価金属で中和されていることが重要である。これにより、前述した本発明の課題を容易に解決することができる。なお、カルボキシル基含有不飽和単量体由来の構成単位が有する全カルボキシル基に対する中和されたカルボキシル基の割合（モル％）(以下「中和率」と称することもある)は、重合体を得る際の重合に用いたカルボキシル基含有不飽和単量体の種類および量と中和に用いた中和剤の種類および量とから、算出して求めるようにすればよい。
前記多価金属としては、例えば、カルシウム（Ｃａ）、マグネシウム（Ｍｇ）、アルミニウム（Ａｌ）、珪素（Ｓｉ）、チタン（Ｔｉ）、鉄（Ｆｅ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ジルコニウム（Ｚｒ）等が挙げられる。これらの中でも特に、カルシウムおよび／またはマグネシウムが好ましい。カルシウムおよび／またはマグネシウムで前記カルボキシル基が中和されていることにより、塗布段階においては一部不溶化（疎水化）していても全体としては水溶性を保持している状態にし、塗膜の形成後はコンクリートや無機質建材等の基材側から供給されるカルシウムイオン等により全体としても水溶性を保持し得ない程度に実質的に完全に不溶化させるように制御できるとともに、強度（硬度）の高い重合体となり、一旦基材に含浸した重合体が強固に固定され、非常に優れた密着性（含浸密着性）を発揮するものとなる上、塗膜全体としても強度に優れたものとなる。
In the polymer of the present invention, it is important that 1 mol% or more of all carboxyl groups of the structural unit derived from the carboxyl group-containing unsaturated monomer which is an essential structural unit is neutralized with a polyvalent metal. It is. Thereby, the subject of the present invention mentioned above can be solved easily. The ratio (mol%) of neutralized carboxyl groups to the total carboxyl groups of the structural unit derived from the carboxyl group-containing unsaturated monomer (hereinafter sometimes referred to as “neutralization rate”) What is necessary is just to calculate and obtain | require from the kind and quantity of the carboxyl group-containing unsaturated monomer used for the polymerization at the time of obtaining, and the kind and quantity of the neutralizing agent used for neutralization.
Examples of the polyvalent metal include calcium (Ca), magnesium (Mg), aluminum (Al), silicon (Si), titanium (Ti), iron (Fe), copper (Cu), zinc (Zn), and zirconium. (Zr) and the like. Of these, calcium and / or magnesium are particularly preferred. By neutralizing the carboxyl group with calcium and / or magnesium, even if it is partially insolubilized (hydrophobized) in the coating stage, it remains water-soluble as a whole and forms a coating film. After that, it can be controlled to be completely insolubilized to the extent that it cannot retain water solubility as a whole by calcium ions supplied from the base material side such as concrete and inorganic building materials, and has high strength (hardness) The polymer once impregnated into the base material is firmly fixed and exhibits excellent adhesion (impregnation adhesion), and the coating film as a whole has excellent strength.
上記多価金属での中和率は、好ましくは３０モル％以上、より好ましくは３５〜９５モル％、さらに好ましくは４０〜９０モル％である。この好ましい中和率の範囲は、カルボキシル基含有不飽和単量体由来の構成単位の含有割合が前述した好ましい範囲を満たすことと共に満たすことが好ましく、具体的には、例えば、前記カルボキシル基含有不飽和単量体由来の構成単位の含有割合が３０モル％以上であり、かつ、前記カルボキシル基含有不飽和単量体由来の構成単位が有する全カルボキシル基のうちの３０モル％以上で前記多価金属での中和がなされていることが好ましい。なお、前記中和は、２種以上の多価金属でなされていてもよく、この場合、それぞれの中和率については、限定はされない。 The neutralization rate with the polyvalent metal is preferably 30 mol% or more, more preferably 35 to 95 mol%, and still more preferably 40 to 90 mol%. The preferable range of the neutralization rate is preferably satisfied together with the content ratio of the structural unit derived from the carboxyl group-containing unsaturated monomer satisfying the above-described preferable range. The content ratio of the structural unit derived from the saturated monomer is 30 mol% or more, and the polyvalent polyvalent content is 30 mol% or more of all the carboxyl groups of the structural unit derived from the carboxyl group-containing unsaturated monomer. It is preferable that neutralization with a metal is performed. The neutralization may be performed with two or more kinds of polyvalent metals, and in this case, the neutralization rate of each is not limited.
本発明の重合体は、必須構成単位であるカルボキシル基含有不飽和単量体由来の構成単位が有する全カルボキシル基のうちの一部が、アンモニア、アミン、カチオン性ポリマー、ならびに、１価のアルカリ金属からなる群より選ばれる少なくとも１種で中和されていることが、水溶性の向上効果や、ｐＨが高くなり防錆効果が得られる点で、好ましい。詳しくは、上記必須構成単位が有する全カルボキシル基のうち、前述したように多価金属で中和されているカルボキシル基以外のカルボキシル基の少なくとも一部が、上記アンモニア等からなる群より選ばれる少なくとも１種で中和されていることが好ましく、該中和率は、上記多価金属での中和率にも依るが、好ましくは上記必須構成単位が有する全カルボキシル基のうちの１〜７０モル％であることが好ましく、より好ましくは５〜６５モル％、さらに好ましくは１０〜６０モル％である。上記中和率が１モル％未満の場合、水中で重合体が析出しやすくなるおそれがあり、７０モル％を超える場合は、耐水性が低下するおそれがある。 In the polymer of the present invention, a part of the total carboxyl groups of the structural unit derived from the carboxyl group-containing unsaturated monomer, which is an essential structural unit, is ammonia, an amine, a cationic polymer, and a monovalent alkali. Neutralization with at least one selected from the group consisting of metals is preferred from the viewpoint of improving the water solubility and increasing the pH and obtaining an antirust effect. Specifically, at least a part of the carboxyl groups other than the carboxyl group neutralized with the polyvalent metal as described above among all the carboxyl groups of the essential structural unit is selected from the group consisting of the ammonia and the like. It is preferably neutralized with one kind, and the neutralization rate depends on the neutralization rate with the polyvalent metal, but preferably 1 to 70 mol of all the carboxyl groups of the essential structural unit. %, More preferably 5 to 65 mol%, still more preferably 10 to 60 mol%. When the said neutralization rate is less than 1 mol%, there exists a possibility that a polymer may precipitate easily in water, and when it exceeds 70 mol%, there exists a possibility that water resistance may fall.
上記アミンとしては、限定はされないが、例えば、例えば、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、トリエチルアミン、モノイソプロピルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、２−アミノメチルプロパノール等が挙げられる。これらは１種のみ用いても２種以上を併用してもよい。
上記カチオン性ポリマーとしては、限定はされないが、例えば、ジメチルアミノエチルメタクリレート等のカチオン性の不飽和単量体を（共）重合した重合体等が挙げられる。これらは１種のみ用いても２種以上を併用してもよい。
Examples of the amine include, but are not limited to, for example, monomethylamine, dimethylamine, trimethylamine, monoethylamine, triethylamine, monoisopropylamine, monoethanolamine, diethanolamine, triethanolamine, and 2-aminomethylpropanol. . These may be used alone or in combination of two or more.
Examples of the cationic polymer include, but are not limited to, a polymer obtained by (co) polymerizing a cationic unsaturated monomer such as dimethylaminoethyl methacrylate. These may be used alone or in combination of two or more.
上記１価のアルカリ金属としては、限定はされないが、例えば、例えば、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）等が挙げられる。これらは１種のみ用いても２種以上を併用してもよい。
本発明の重合体の重量平均分子量は、限定はされないが、１，０００〜１００，０００であることが好ましく、より好ましくは２，０００〜９０，０００、さらに好ましくは３，０００〜８０，０００、特に好ましくは５，０００〜５０，０００である。上記重量平均分子量が１，０００未満であると、水性シーラー等の各種用途に用いた場合に機械的強度が低下するおそれがあり、１００，０００を超えると、水性シーラー等のように水に溶解させて用いる用途に用いた場合に粘度が高くなり、ハンドリング性が低下したり均一に塗工できない等のおそれがある。
Although it does not limit as said monovalent alkali metal, For example, lithium (Li), sodium (Na), potassium (K) etc. are mentioned, for example. These may be used alone or in combination of two or more.
The weight average molecular weight of the polymer of the present invention is not limited, but is preferably 1,000 to 100,000, more preferably 2,000 to 90,000, still more preferably 3,000 to 80,000. Particularly preferred is 5,000 to 50,000. If the weight average molecular weight is less than 1,000, the mechanical strength may decrease when used in various applications such as an aqueous sealer. If it exceeds 100,000, it dissolves in water like an aqueous sealer. When used in applications, the viscosity becomes high, and there is a possibility that handling properties may be lowered or coating may not be performed uniformly.
本発明の重合体の製造方法について、以下に説明する。
本発明の重合体の製造方法としては、上述の特徴を有するポリカルボン酸系重合体が得られる方法であれば、限定はされず、公知の各種重合方法を採用することができるが、なかでも、水性溶媒中において前述したカルボキシル基含有不飽和単量体を必須とする単量体成分を均一攪拌重合する方法が好ましい。
使用する単量体成分は、前記カルボキシル基含有不飽和単量体を必須とするものであればよく、必要に応じ、前記他の単量体を含んでいてもよい。単量体成分中、カルボキシル基含有不飽和単量体の配合割合は、限定はされないが、単量体成分全体に対し、３０モル％以上であることが好ましく、より好ましくは５０モル％以上、さらに好ましくは７０モル％以上であり、特に好ましくは１００モル％である。上記含有割合が３０モル％未満であると、そのほかの共重合組成にもよるが、水溶性を保てなくなるおそれがある
単量体成分の水性溶媒中への添加方法は、限定はされないが、単量体成分全体に対し７０重量％以上を、実質的に連続的に滴下することで反応系に添加することが好ましく、より好ましくは９０重量％以上、さらに好ましくは全量である。上記連続滴下量の割合が、７０重量％未満であると（例えば初期仕込量が３０重量％を超える場合等）、重合初期に単量体成分がブロック的に重合したり、高分子量化したりするおそれがあり、得られる重合体の物性の制御が困難となるおそれがある。上記添加の際の滴下時間は、限定はされないが、３０〜３６０分間であることが好ましく、より好ましくは６０〜２４０分間、さらに好ましくは９０〜１８０分間である。上記滴下時間が３０分間未満であると、ブロック的に重合するおそれがあり、３６０分間を超えると、製造施設・装置の点から制限を受けるだけでなく、製造費の上昇を招くおそれがある。
The manufacturing method of the polymer of this invention is demonstrated below.
The method for producing the polymer of the present invention is not limited as long as the polycarboxylic acid polymer having the above-described characteristics is obtained, and various known polymerization methods can be adopted. A method of uniformly stirring and polymerizing a monomer component essentially containing the above-described carboxyl group-containing unsaturated monomer in an aqueous solvent is preferable.
The monomer component to be used is not limited as long as it contains the carboxyl group-containing unsaturated monomer as essential, and may contain other monomers as necessary. In the monomer component, the proportion of the carboxyl group-containing unsaturated monomer is not limited, but is preferably 30 mol% or more, more preferably 50 mol% or more, based on the entire monomer component. More preferably, it is 70 mol% or more, Most preferably, it is 100 mol%. If the content is less than 30 mol%, depending on the other copolymer composition, there is a possibility that water solubility may not be maintained. The method for adding the monomer component to the aqueous solvent is not limited, It is preferable to add 70% by weight or more with respect to the whole monomer component to the reaction system by dripping substantially continuously, more preferably 90% by weight or more, and still more preferably the total amount. When the ratio of the continuous dripping amount is less than 70% by weight (for example, when the initial charge exceeds 30% by weight, etc.), the monomer component is polymerized in a block manner or increased in molecular weight at the initial stage of polymerization. There is a possibility that control of physical properties of the resulting polymer may be difficult. The dropping time at the time of the addition is not limited, but is preferably 30 to 360 minutes, more preferably 60 to 240 minutes, and still more preferably 90 to 180 minutes. If the dropping time is less than 30 minutes, there is a risk of polymerizing in a block, and if it exceeds 360 minutes, it is not only restricted from the viewpoint of the production facility / apparatus, but also may increase the manufacturing cost.
単量体成分を重合させるために用い得るラジカル重合開始剤としては、限定はされず、少なくとも１種の過硫酸塩と過酸化水素との併用系が好ましい。また必要に応じ、連鎖移動剤および多価金属イオン（開始剤の分解促進剤として働くもの）のいずれか１種を用いるか、または、両方を同時に用いてもよい。上記過硫酸塩としては、例えば、過硫酸ナトリウム、過硫酸カリウムおよび過硫酸アンモニウム等を挙げることができ、好ましくは過硫酸ナトリウムである。
上記過硫酸塩の添加量は、単量体成分１モルに対し１．０〜５．０ｇが好ましく、２．０〜４．０ｇであることがより好ましい。過硫酸塩の添加量が１．０ｇ未満であると、得られる重合体が高分子量化するおそれがあり、添加量が多すぎると、過硫酸塩の効果が添加量に伴うほど得られなくなり、さらに、得られる重合体の純度が低下するなど悪影響を及ぼすおそれがある。
The radical polymerization initiator that can be used for polymerizing the monomer component is not limited, and a combined system of at least one persulfate and hydrogen peroxide is preferable. Further, if necessary, any one of a chain transfer agent and a polyvalent metal ion (acting as an initiator decomposition accelerator) may be used, or both may be used simultaneously. Examples of the persulfate include sodium persulfate, potassium persulfate, and ammonium persulfate, and sodium persulfate is preferable.
The amount of the persulfate added is preferably 1.0 to 5.0 g and more preferably 2.0 to 4.0 g with respect to 1 mol of the monomer component. If the amount of persulfate added is less than 1.0 g, the resulting polymer may have a high molecular weight. If the amount added is too large, the effect of persulfate cannot be obtained as the amount added increases. Furthermore, there is a risk of adverse effects such as a decrease in the purity of the resulting polymer.
過酸化水素の添加量は、単量体成分１モルに対し２．０〜１０．０ｇが好ましく、３．０〜８．０ｇであることがより好ましい。過酸化水素の添加量が２．０ｇ未満であると、得られる重合体が高分子量化するおそれがあり、１０．０ｇを超えると、過酸化水素の効果が添加量に伴うほど得られなくなり、さらに残存する過酸化水素量が多くなるなどの悪影響を及ぼすおそれがある。
過硫酸塩および過酸化水素の添加比率は、重量比で、過酸化水素の添加量を１としたときに、過硫酸塩の添加量が０．１〜５．０であることが好ましく、０．５〜３．０であることがより好ましい。上記添加比率が０．１未満であると、得られる重合体が高分子量化するおそれがあり、５．０を超えると、過硫酸塩の添加による分子量低下の効果が添加に伴うほど得られない状態で、重合反応系において過硫酸塩が無駄に消費されることになるおそれがある。
The amount of hydrogen peroxide added is preferably 2.0 to 10.0 g, more preferably 3.0 to 8.0 g, per 1 mol of the monomer component. If the added amount of hydrogen peroxide is less than 2.0 g, the resulting polymer may have a high molecular weight, and if it exceeds 10.0 g, the effect of hydrogen peroxide cannot be obtained as the added amount increases. Furthermore, there is a risk of adverse effects such as an increase in the amount of remaining hydrogen peroxide.
The addition ratio of persulfate and hydrogen peroxide is preferably a weight ratio of 0.1 to 5.0 when the addition amount of hydrogen peroxide is 1. More preferably, it is 5-3.0. If the addition ratio is less than 0.1, the resulting polymer may have a high molecular weight, and if it exceeds 5.0, the effect of lowering the molecular weight due to the addition of persulfate cannot be obtained as much as the addition. In this state, the persulfate may be wasted in the polymerization reaction system.
用い得るラジカル重合開始剤としては、上記過硫酸塩および過酸化水素以外に、他のラジカル重合開始剤を併用してもよい。他のラジカル重合開始剤としては、例えば、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩、４，４’−アゾビス−４−シアノバレリン酸、アゾビスイソブチロニトリル、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）等のアゾ系化合物、過酸化ベンゾイル、過酸化ラウロイル、過酢酸、ジ−ｔ−ブチルパーオキサイド、クメンヒドロパーオキサイド等の有機過酸化物があげられる。これらは１種のみ用いても２種以上を併用してもよく、限定はされない。
連鎖移動剤は、重合に悪影響を及ぼさない範囲内で、得られる重合体の分子量調整剤として、必要に応じ、ラジカル重合開始剤と併用することが好ましい。
As the radical polymerization initiator that can be used, in addition to the persulfate and hydrogen peroxide, other radical polymerization initiators may be used in combination. Examples of other radical polymerization initiators include 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis-4-cyanovaleric acid, azobisisobutyronitrile, 2,2 ′. Organic compounds such as azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide Can be given. These may be used alone or in combination of two or more, and are not limited.
The chain transfer agent is preferably used in combination with a radical polymerization initiator, if necessary, as a molecular weight regulator for the resulting polymer within a range that does not adversely affect the polymerization.
連鎖移動剤としては、例えば、亜硫酸塩、重亜硫酸塩、次亜リン酸塩、メルカプトプロピオン酸およびチオグリコール酸等が挙げられる。これらは１種のみ用いても２種以上を併用してもよい。
連鎖移動剤の使用量は、重量比で、ラジカル重合開始剤量の２倍以内であることが好ましい。２倍を超えて使用しても、もはや添加量に見合った添加効果は得られず、却って重合体の純分の低下を招くおそれがある。連鎖移動剤の添加方法は、滴下による場合は、その滴下時間は、限定はされず、適宜設定すればよい。
多価金属イオンは、ラジカル重合開始剤の分解促進剤として、必要に応じ、該開始剤と併用することが好ましい。
Examples of the chain transfer agent include sulfite, bisulfite, hypophosphite, mercaptopropionic acid and thioglycolic acid. These may be used alone or in combination of two or more.
The amount of the chain transfer agent used is preferably within 2 times the amount of the radical polymerization initiator by weight. Even if it is used in excess of 2 times, the effect of addition corresponding to the addition amount can no longer be obtained, and there is a possibility that the pure content of the polymer is reduced instead. In the case of adding a chain transfer agent by dropping, the dropping time is not limited and may be set as appropriate.
The polyvalent metal ion is preferably used in combination with the initiator as necessary as a decomposition accelerator for the radical polymerization initiator.
多価金属イオンとしては、Ｆｅ２＋、Ｆｅ３＋、Ｃｕ２＋、Ｃｕ＋、Ｖ２＋、Ｖ３＋、ＶＯ２＋等が有効なものとして挙げられ、なかでもＦｅ２＋、Ｆｅ３＋が好ましい。これらは１種のみ用いても２種以上を併用してもよい。
多価金属イオンの使用量は、反応液全量に対し１００ｐｐｍ以下が好ましく、より好ましくは７０ｐｐｍ以下、さらに好ましくは５０ｐｐｍ以下、特に好ましくは３０ｐｐｍ以下である。上記使用量が１００ｐｐｍを超えると、添加した効果はもはや見られず、また得られる重合体に着色の問題が生じるおそれがある。多価金属イオンの添加方法は、限定はされず、単量体の滴下終了前までに添加することが好ましく、全量初期仕込することがより好ましい。
Examples of the polyvalent metal ions include Fe 2+ , Fe 3+ , Cu 2+ , Cu + , V 2+ , V 3+ , VO 2+, and the like, among which Fe 2+ and Fe 3+ are preferable. These may be used alone or in combination of two or more.
The amount of polyvalent metal ions used is preferably 100 ppm or less, more preferably 70 ppm or less, still more preferably 50 ppm or less, particularly preferably 30 ppm or less, based on the total amount of the reaction solution. When the amount used exceeds 100 ppm, the added effect is no longer seen, and there is a possibility that coloring problems may occur in the resulting polymer. The method for adding the polyvalent metal ion is not limited, and it is preferably added before the end of dropping of the monomer, and more preferably the whole amount is initially charged.
多価金属イオンの供給源としては、限定はされず、重合反応系内で多価金属イオンとしてイオン化し得るものであれば、どのような金属化合物や金属を用いることもできる。例えば、オキシ三塩化バナジウム、三塩化バナジウム、シュウ酸バナジウム、硫酸バナジウム、無水バナジン酸、メタバナジン酸アンモニウム、硫酸アンモニウムハイポバナダス［（ＮＨ４）２ＳＯ４・ＶＳＯ４・６Ｈ２Ｏ］、硫酸アンモニウムバナダス［（ＮＨ４）Ｖ（ＳＯ４）２・１２Ｈ２Ｏ］、酢酸銅（II）、臭化銅（II）、銅（II）アセチルアセテート、塩化第二銅、塩化銅アンモニウム、炭酸銅、塩化銅（II）、クエン酸銅（II）、ギ酸銅（II）、水酸化銅（II）、硝酸銅、ナフテン酸銅、オレイン酸銅（II）、マレイン酸銅、リン酸銅、硫酸銅（II）、塩化第一銅、シアン化銅（Ｉ）、ヨウ化銅、酸化銅（Ｉ）、チオシアン酸銅、鉄アセチルアセトナート、クエン酸鉄アンモニウム、シュウ酸第二鉄アンモニウム、硫酸第一鉄アンモニウム、硫酸第二鉄アンモニウム、クエン酸鉄、フマル酸鉄、マレイン酸鉄、乳酸第一鉄、硝酸第二鉄、鉄ペンタカルボニル、リン酸第二鉄、ピロリン酸第二鉄等の水溶性金属塩、五酸化バナジウム、酸化銅（II）、酸化第一鉄、酸化第二鉄などの金属酸化物、硫化銅（II）、硫化鉄などの金属硫化物、銅粉末および鉄粉末等が挙げられる。また、多価金属イオンの供給源としては、装置自体から溶出する金属であってもよい。 The supply source of the polyvalent metal ion is not limited, and any metal compound or metal can be used as long as it can be ionized as the polyvalent metal ion in the polymerization reaction system. For example, vanadium oxytrichloride, vanadium trichloride, vanadium oxalate, vanadium sulfate, vanadic anhydride, ammonium metavanadate, ammonium sulfate hypo-nosed Das [(NH 4) 2 SO 4 · VSO 4 · 6H 2 O], ammonium sulfate nosed Das [(NH 4 ) V (SO 4 ) 2 · 12H 2 O], copper (II) acetate, copper (II) bromide, copper (II) acetyl acetate, cupric chloride, ammonium copper chloride, copper carbonate, chloride Copper (II), copper citrate (II), copper formate (II), copper hydroxide (II), copper nitrate, copper naphthenate, copper oleate, copper maleate, copper phosphate, copper sulfate ( II), cuprous chloride, copper (I) cyanide, copper iodide, copper (I) oxide, copper thiocyanate, iron acetylacetonate, iron ammonium citrate, ferric ammonium oxalate, ferrous sulfate Water-soluble metals such as ammonium, ammonium ferric sulfate, iron citrate, iron fumarate, iron maleate, ferrous lactate, ferric nitrate, iron pentacarbonyl, ferric phosphate, ferric pyrophosphate Examples include salts, metal oxides such as vanadium pentoxide, copper (II) oxide, ferrous oxide, and ferric oxide, metal sulfides such as copper (II) sulfide and iron sulfide, copper powder, and iron powder. . In addition, as a supply source of polyvalent metal ions, a metal eluted from the apparatus itself may be used.
重合反応においては、上述したラジカル重合開始剤等の各種添加剤以外に、重合反応を阻害せず、得られる重合体の物性を阻害しない範囲で、他の添加剤等を適宜用いてもよい。
前述したように、本発明の重合体は、必須単量体成分であるカルボキシル基含有不飽和単量体に由来する構成単位が有する全カルボキシル基のうち特定の割合のカルボキシル基が、多価金属、好ましくはカルシウムおよび／またはマグネシウムで中和されている。
上記中和は、(ｉ)単量体成分を反応器に供給する前に、カルボキシル基含有不飽和単量体に対して予め行われていてもよいし、(ｉｉ)単量体成分と中和剤とを別々に反応器に供給し、反応器内でカルボキシル基含有不飽和単量体に対して行われてもよいし（重合反応中の中和も含む。）、(ｉｉｉ)重合反応後に反応器内に中和剤を供給し、得られた重合体に対して行われてもよく、限定はされない。また、最終的に所望の中和率に調整できれば、上記(ｉ)〜(ｉｉｉ)を組み合わせて行うようにしてもよい。
In the polymerization reaction, in addition to the various additives such as the radical polymerization initiator described above, other additives may be appropriately used as long as the polymerization reaction is not inhibited and the physical properties of the resulting polymer are not inhibited.
As described above, the polymer of the present invention has a specific proportion of carboxyl groups among all the carboxyl groups of the structural unit derived from the carboxyl group-containing unsaturated monomer which is an essential monomer component. Preferably neutralized with calcium and / or magnesium.
The neutralization may be performed in advance on the carboxyl group-containing unsaturated monomer before (i) supplying the monomer component to the reactor, or (ii) The summing agent may be separately supplied to the reactor, and the reaction may be performed on the carboxyl group-containing unsaturated monomer in the reactor (including neutralization during the polymerization reaction), or (iii) polymerization reaction A neutralizing agent may be supplied into the reactor later, and the resultant polymer may be used without any limitation. Moreover, if it can adjust finally to a desired neutralization rate, you may make it carry out combining said (i)-(iii).
該中和に用い得る中和剤としては、限定はないが、上記多価金属のうち、例えば、カルシウムにより中和する場合は、例えば、水酸化カルシウム、塩化カルシウム、酸化カルシウム等が挙げられ、マグネシウムにより中和する場合は、例えば、水酸化マグネシウム、塩化マグネシウム等が挙げられ、アルミニウムより中和する場合は、水酸化アルミニウム、塩化アルミニウム等が挙げられ、珪素より中和する場合は、珪素粉末等が挙げられ、チタンより中和する場合は、塩化チタン等が挙げられ、鉄より中和する場合は、水酸化鉄、塩化第一鉄、塩化第二鉄等が挙げられ、銅より中和する場合は、水酸化銅、塩化第一銅、塩化第二銅等が挙げられ、亜鉛より中和する場合は、水酸化亜鉛、塩化亜鉛等が挙げられ、ジルコニウムより中和する場合は、水酸化ジルコニウム等が挙げられる。 The neutralizing agent that can be used for the neutralization is not limited. Among the polyvalent metals, for example, when neutralizing with calcium, examples include calcium hydroxide, calcium chloride, calcium oxide, In the case of neutralizing with magnesium, for example, magnesium hydroxide, magnesium chloride and the like can be mentioned. In the case of neutralizing from aluminum, aluminum hydroxide, aluminum chloride and the like can be mentioned, and when neutralizing from silicon, silicon powder can be used. When neutralizing from titanium, examples include titanium chloride. When neutralizing from iron, examples include iron hydroxide, ferrous chloride, ferric chloride, and the like. In the case of neutralizing from zinc, zinc hydroxide, zinc chloride, etc. are mentioned in the case of neutralizing from zirconium. Include zirconium hydroxide and the like.
前記多価金属で中和する際に用いる中和剤の使用量は、限定はされず、所望の中和率の重合体が得られるよう適宜設定すればよい。
また、前述したように、本発明の重合体が、必須単量体成分であるカルボキシル基含有不飽和単量体に由来する構成単位が有する全カルボキシル基の一部が、アンモニア、アミン、カチオン性ポリマー、ならびに、１価のアルカリ金属からなる群より選ばれる少なくとも１種で中和されている場合についても、該中和は、上記(ｉ)〜（ｉｉｉ)で示した多価金属での中和と同様に行うことができる。
上記アンモニア等からなる群より選ばれる少なくとも１種での中和に用い得る中和剤（他の中和剤）としては、アンモニアにより中和する場合は、例えば、アンモニア水（濃度は限定されないが、好ましくは２５重量％程度）等が挙げられ、アミンにより中和する場合は、例えば、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、トリエチルアミン、モノイソプロピルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、２−アミノメチルプロパノール等が挙げられ、カチオン性ポリマーにより中和する場合は、例えば、ジメチルアミノエチルメタクリレート等のカチオン性の不飽和単量体を（共）重合した重合体の水溶液等が挙げられ、１価のアルカリ金属により中和する場合は、例えば、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、水酸化カリウム、炭酸カリウム、炭酸水素カリウム、水酸化リチウム、炭酸リチウム、水素リチウム等が挙げられる。
The amount of the neutralizing agent used when neutralizing with the polyvalent metal is not limited, and may be set as appropriate so as to obtain a polymer having a desired neutralization rate.
In addition, as described above, in the polymer of the present invention, a part of all carboxyl groups of the structural unit derived from the carboxyl group-containing unsaturated monomer which is an essential monomer component is ammonia, amine, cationic Also in the case where the polymer is neutralized with at least one selected from the group consisting of monovalent alkali metals, the neutralization is performed in the polyvalent metals shown in the above (i) to (iii). It can be done in the same way as the sum.
As a neutralizing agent (other neutralizing agent) that can be used for neutralization with at least one selected from the group consisting of ammonia and the like, when neutralizing with ammonia, for example, aqueous ammonia (concentration is not limited) In the case of neutralization with an amine, for example, monomethylamine, dimethylamine, trimethylamine, monoethylamine, triethylamine, monoisopropylamine, monoethanolamine, diethanolamine, triethanolamine, In the case of neutralizing with a cationic polymer, for example, an aqueous solution of a polymer obtained by (co) polymerizing a cationic unsaturated monomer such as dimethylaminoethyl methacrylate is used. Example when neutralizing with monovalent alkali metal If, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, lithium hydroxide, lithium carbonate, lithium hydrogen and the like.
上記他の中和剤の使用量は、限定はされず、所望の中和率の重合体が得られるよう適宜設定すればよい。
重合反応に用い得る水性溶媒としては、重合に用いる単量体の溶媒への溶解性向上のため、必要に応じて重合に悪影響を及ぼさない範囲で有機溶媒を適宜含んでいてもよいが、溶媒全体の８０重量％以上が水であることが好ましく、水単独であることが特に好ましい。
上記有機溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコール等の低級アルコール類、アセトン、メチルエチルケトン、ジエチルケトン等の低級ケトン類；ジメチルエーテル、ジエチルエーテル、ジオキサン等のエーテル類；ジメチルホルムアルデヒド等のアミド類；等が挙げられる。これらは１種のみ用いても２種以上を併用してもよいが、好ましくはイソプロピルアルコールである。イソプロピルアルコールには連鎖移動剤としての効果があり、重合体をより低分子量化することができる。これらの有機溶媒は重合終了後に除去してもよい。
The usage-amount of said other neutralizing agent is not limited, What is necessary is just to set suitably so that the polymer of a desired neutralization rate may be obtained.
The aqueous solvent that can be used for the polymerization reaction may optionally contain an organic solvent as long as it does not adversely affect the polymerization, as necessary, in order to improve the solubility of the monomer used for the polymerization in the solvent. It is preferable that 80% by weight or more of the total is water, and water is particularly preferable.
Examples of the organic solvent include lower alcohols such as methanol, ethanol and isopropyl alcohol, lower ketones such as acetone, methyl ethyl ketone and diethyl ketone; ethers such as dimethyl ether, diethyl ether and dioxane; amides such as dimethylformaldehyde; Etc. These may be used alone or in combination of two or more, preferably isopropyl alcohol. Isopropyl alcohol has an effect as a chain transfer agent and can lower the molecular weight of the polymer. These organic solvents may be removed after completion of the polymerization.
重合時における温度は、限定はされないが、例えば、６０℃以上であることが好ましく、より好ましくは７０℃以上、さらに好ましくは重合溶媒の沸点近傍であり、最も好ましくは重合溶媒の沸点である。重合時の温度が６０℃未満であると、重合開始剤の分解効率が悪くなり、得られる重合体における単量体成分の残存量が多くなるおそれがある。また、沸点またはその近傍の温度で重合を行うことは、温度制御が非常に容易となり、そのため重合の再現性がよく、得られる重合体においても品質的に非常に安定したものとなり好ましい。ただし、大きな発泡がある場合は沸点未満が好ましい。
得られる重合体の最終濃度は、限定はされないが、例えば、１０〜７０重量％が好ましく、より好ましくは２０〜６５重量％、さらに好ましくは３０〜６０重量％であり、この範囲を満たすように滴下する単量体成分等の濃度調整を行う。得られる重合体の最終濃度が上記範囲未満であると、結果的に重合中の濃度が非常に低くなるので、単量体成分の重合性が非常に悪くなり得られる重合体中における単量体成分の残存量が非常に多くなるおそれがあるほか、輸送等の効率や生産性も低くなり経済的な面からも好ましくない。一方、得られる重合体の最終濃度が上記範囲を超えると、結果的に重合中の濃度が非常に高くなるため、反応液が非常に高粘度になり、均一重合とならず、また非常に高分子量化するおそれがあるほか、得られる重合体の溶液粘度が非常に高くなりハンドリング性等の面からも好ましくない。なお、重合終了後の重合体の最終的な濃度は濃縮や希釈により適宜調整することができる。
Although the temperature at the time of superposition | polymerization is not limited, For example, it is preferable that it is 60 degreeC or more, More preferably, it is 70 degreeC or more, More preferably, it is the boiling point vicinity of a polymerization solvent, Most preferably, it is a boiling point of a polymerization solvent. When the polymerization temperature is less than 60 ° C., the decomposition efficiency of the polymerization initiator is deteriorated, and the residual amount of monomer components in the resulting polymer may be increased. In addition, it is preferable to perform polymerization at a temperature at or near the boiling point because the temperature control becomes very easy, and therefore the reproducibility of the polymerization is good, and the obtained polymer is very stable in quality. However, when there is large foaming, it is preferably less than the boiling point.
The final concentration of the obtained polymer is not limited, but is preferably 10 to 70% by weight, more preferably 20 to 65% by weight, still more preferably 30 to 60% by weight, so as to satisfy this range. The concentration of the monomer component to be dropped is adjusted. If the final concentration of the obtained polymer is less than the above range, the resulting concentration during polymerization becomes very low, so that the monomer component polymerizability becomes very poor and the monomer in the polymer can be obtained. In addition to the possibility that the remaining amount of the components will be very large, the efficiency and productivity of transportation and the like will be lowered, which is not preferable from the economical viewpoint. On the other hand, if the final concentration of the obtained polymer exceeds the above range, the concentration during polymerization will become very high as a result, so that the reaction solution will have a very high viscosity and will not be homogeneously polymerized. In addition to the possibility of increasing the molecular weight, the resulting polymer has a very high solution viscosity, which is not preferable in terms of handling properties. The final concentration of the polymer after completion of the polymerization can be appropriately adjusted by concentration or dilution.
重合時における圧力は、限定はされず、加圧、常圧（大気圧）、減圧いずれでもよく場合により適宜設定すればよいが、常圧が好ましい。
本発明の重合体の用途は、限定はされないが、洗剤ビルダー、スケール防止剤、キレート剤、セメント減水剤、インキ用バインダー、フィルム成形品、パルプ成形品、シート成形品、ラミネート用材料、例えば、車両用、プラスチック成形品用、家電品用、鋼製品、大型構造物、航空機用、建材用、建築用、瓦用、木工用などの上塗りもしくは中塗り水性塗料や水性シーラー等に有用であり、特に、水性シーラーの成分として用いた場合、コンクリートや無機質建材等の基材に対する含浸密着性に優れ、かつ、長期間使用しても再溶出したり剥がれたりせず良好な耐水性を発揮する水性シーラーを得させることのできるため、特に好ましい。
The pressure at the time of polymerization is not limited, and may be any of pressurization, normal pressure (atmospheric pressure), and reduced pressure, and may be appropriately set depending on the case, but normal pressure is preferable.
Applications of the polymer of the present invention are not limited, but include detergent builders, scale inhibitors, chelating agents, cement water reducing agents, ink binders, film molded products, pulp molded products, sheet molded products, laminating materials such as Useful for overcoating or intermediate coating water-based paints and water-based sealers for vehicles, plastic molded products, household appliances, steel products, large structures, aircraft, building materials, construction, roof tiles, woodwork, etc. In particular, when used as a component of an aqueous sealer, it has excellent impregnation adhesion to substrates such as concrete and inorganic building materials, and exhibits good water resistance without re-elution or peeling even after long-term use. Since a sealer can be obtained, it is particularly preferable.
〔水性シーラー〕
本発明にかかる水性シーラーは、前述したように、上記本発明にかかるポリカルボン酸系重合体と水性媒体とを含むものである。詳しくは、上記本発明にかかるポリカルボン酸系重合体が、水性媒体中に溶解していることが好ましい。上記本発明にかかるポリカルボン酸系重合体を含むことにより、コンクリートや無機質建材等の基材に対する含浸密着性に優れ、かつ、長期間使用しても再溶出したり剥がれたりせず良好な耐水性を発揮するものとなる。
ポリカルボン酸系重合体の詳細については、上記本発明にかかるポリカルボン酸系重合体の説明が同様に適用できる。
(Water-based sealer)
As described above, the aqueous sealer according to the present invention includes the polycarboxylic acid polymer according to the present invention and an aqueous medium. Specifically, the polycarboxylic acid polymer according to the present invention is preferably dissolved in an aqueous medium. By including the polycarboxylic acid-based polymer according to the present invention, it has excellent impregnation adhesion to substrates such as concrete and inorganic building materials, and has good water resistance without re-elution or peeling even after long-term use. It will exhibit the sex.
About the detail of a polycarboxylic acid type polymer, the description of the polycarboxylic acid type polymer concerning the said invention is applicable similarly.
水性媒体としては、限定はされず、溶解性向上のため、必要に応じ、長期の耐水性に悪影響を及ぼさない範囲で、有機溶媒を適宜含んでいてもよいが、全体の８０重量％以上が水であることが好ましく、水単独であることが特に好ましい。
本発明の水性シーラーにおいては、ポリカルボン酸系重合体の配合割合は、限定はされないが、水性シーラー全体に対し、２〜６０重量％であることが好ましく、より好ましくは４〜５０重量％である。上記配合割合が２重量％未満であると、含浸密着性が低下するおそれがあり、６０重量％を超えると、水性シーラーの粘度が高くなり、塗布が困難となるおそれがある。
The aqueous medium is not limited, and may contain an organic solvent as appropriate within a range that does not adversely affect long-term water resistance, if necessary, in order to improve solubility. Water is preferred and water alone is particularly preferred.
In the aqueous sealer of the present invention, the blending ratio of the polycarboxylic acid-based polymer is not limited, but is preferably 2 to 60% by weight, more preferably 4 to 50% by weight based on the entire aqueous sealer. is there. If the blending ratio is less than 2% by weight, the impregnation adhesion may be reduced, and if it exceeds 60% by weight, the viscosity of the aqueous sealer may be increased and application may be difficult.
本発明のシーラーは、シーラーとしての耐水性の向上や、粘性等の取り扱い性の調整等を行うために、樹脂エマルションを含んでいてもよい。樹脂エマルションとしては、例えば、アクリル系エマルション、アクリルスチレン系エマルション、塩化ビニル系エマルション、塩化ビニリデン系エマルション、酢酸ビニル系エマルション、エチレン酢酸ビニル系エマルション、ポリウレタン系エマルション、アルキド樹脂系エマルション、ビスフェノール型エポキシエマルション等が挙げられる。これらは１種のみ用いても２種以上を併用してもよい。
樹脂エマルションを含む場合、その配合割合は、固形分全体に対し、固形分基準で３０〜９０重量％であることが好ましく、より好ましくは４０〜８０重量％である。
The sealer of the present invention may contain a resin emulsion in order to improve water resistance as a sealer, adjust handling properties such as viscosity, and the like. Examples of the resin emulsion include acrylic emulsion, acrylic styrene emulsion, vinyl chloride emulsion, vinylidene chloride emulsion, vinyl acetate emulsion, ethylene vinyl acetate emulsion, polyurethane emulsion, alkyd resin emulsion, bisphenol type epoxy emulsion. Etc. These may be used alone or in combination of two or more.
When the resin emulsion is included, the blending ratio is preferably 30 to 90% by weight, more preferably 40 to 80% by weight based on the solid content with respect to the entire solid content.
本発明のシーラーは、上記各種構成成分以外に、顔料、分散剤、表面調整剤、増粘剤、酸化防止剤、紫外線防止剤、消泡剤等の各種添加剤を、本発明の水性シーラーの効果が損なわれない範囲で、適宜含んでいてもよい。
前記顔料としては、例えば、有機系顔料では、アゾキレート系顔料、不溶性アゾ系顔料、縮合アゾ系顔料、フタロシアニン系顔料、インジゴ顔料、ペリノン系顔料、ペリレン系顔料、ジオキサン系顔料、キナクリドン系顔料、イソインドリノン系顔料、金属錯体顔料等が挙げられ、無機系顔料では、黄鉛、黄色酸化鉄、ベンガラ、カーボンブラック、二酸化チタン等の着色顔料や、タルク、クレー、硫酸バリウム、炭酸カルシウム等の体質顔料等が挙げられ、これらは１種のみ用いても２種以上を併用してもよい。
The sealer of the present invention contains various additives such as pigments, dispersants, surface conditioners, thickeners, antioxidants, UV inhibitors, antifoaming agents, etc. It may be included as long as the effect is not impaired.
Examples of the pigment include, for example, an azo chelate pigment, an insoluble azo pigment, a condensed azo pigment, a phthalocyanine pigment, an indigo pigment, a perinone pigment, a perylene pigment, a dioxane pigment, a quinacridone pigment, and an organic pigment. Indolinone pigments, metal complex pigments, etc., inorganic pigments include colored pigments such as yellow lead, yellow iron oxide, bengara, carbon black, titanium dioxide, and constitutions such as talc, clay, barium sulfate, calcium carbonate A pigment etc. are mentioned, These may use only 1 type or may use 2 or more types together.
以下に、実施例によって本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。以下、特に断りのない限り、「重量部」を単に「部」と、「重量％」を単に「％」と記すものとする。
各実施例および比較例における重量平均分子量（Ｍｗ）の測定は、ＧＰＣ（ゲルパーミュエーションクロマトグラフィー）で分析することにより行った。用いた装置や測定条件などは以下の通りである。
ＧＰＣカラム：昭和電工製「ＧＦ−７ＭＨＱ」
移動相：リン酸水素二ナトリウム１２水和物３４．５ｇおよびリン酸二水素ナトリウム２水和物４６．２ｇ（いずれも試薬特級）に純水を加えて全量を５０００ｇとし、その後０．４５μｍのメンブランフィルターでろ過した水溶液
検出器：ウォーターズ製「モデル４８１型」
検出波長：ＵＶ２１４ｎｍ
ポンプ：（株）日立製作所製「Ｌ−７１１０」
流量：０．５ｍＬ／分
温度：３５℃
検量線：ポリアクリル酸ナトリウム標準サンプル（創和科学製）を用いて作成した
〔実施例１〕
還流冷却管および攪拌機を備えた容量５ＬのＳＵＳ３１６製セパラブルフラスコに、イオン交換水１６００ｇを仕込み、攪拌下１００℃に昇温した後、８０％アクリル酸水溶液（以下「８０％ＡＡ」と称す）３６０ｇ（アクリル酸４モル）と、１５％過硫酸アンモニウム水溶液（以下「１５％ＡＰＳ」と称す）２１３．３ｇ（アクリル酸１モルに対して過硫酸アンモニウム８ｇ）とを、それぞれ別の滴下口から滴下した。このとき、滴下開始は同時とし、それぞれの滴下時間は、８０％ＡＡが１８０分間、１５％ＡＰＳが１８５分間となるようにするとともに、滴下の間、還流状態を維持するように加熱して行った。その後、８０％ＡＡの滴下終了から３０分間、さらに還流状態を維持して重合を完結させたのち、反応溶液を室温まで冷却した。続いて、真空ポンプにて２００ｍｍＨｇまで減圧して約６５℃で約９０分間濃縮を行うことにより所定量の水分を除去し、固形分濃度４０％の重合体水溶液（１）を得た。該重合体水溶液（１）中のポリマーの重量平均分子量（Ｍｗ）は５，０００であった。
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. Hereinafter, unless otherwise specified, “parts by weight” is simply referred to as “parts”, and “% by weight” is simply referred to as “%”.
The measurement of the weight average molecular weight (Mw) in each Example and a comparative example was performed by analyzing by GPC (gel permeation chromatography). The equipment and measurement conditions used are as follows.
GPC column: Showa Denko "GF-7MHQ"
Mobile phase: 34.5 g of disodium hydrogen phosphate dodecahydrate and 46.2 g of sodium dihydrogen phosphate dihydrate (both are reagent-grade) to make pure water to 5000 g, and then 0.45 μm Aqueous solution filtered with membrane filter Detector: Waters Model 481
Detection wavelength: UV214nm
Pump: “L-7110” manufactured by Hitachi, Ltd.
Flow rate: 0.5 mL / min Temperature: 35 ° C
Calibration curve: prepared using a sodium polyacrylate standard sample (manufactured by Sowa Kagaku) [Example 1]
A 5 L SUS316 separable flask equipped with a reflux condenser and a stirrer was charged with 1600 g of ion exchange water, heated to 100 ° C. with stirring, and then 80% aqueous acrylic acid solution (hereinafter referred to as “80% AA”). 360 g (4 mol of acrylic acid) and 213.3 g of 15% aqueous ammonium persulfate solution (hereinafter referred to as “15% APS”) (8 g of ammonium persulfate with respect to 1 mol of acrylic acid) were dropped from separate dripping ports. . At this time, the dripping is started at the same time, and each dripping time is set so that 80% AA is 180 minutes and 15% APS is 185 minutes, and heating is performed so as to maintain a reflux state during the dropping. It was. Thereafter, after completion of the dropwise addition of 80% AA, the reflux state was maintained for 30 minutes to complete the polymerization, and then the reaction solution was cooled to room temperature. Subsequently, the pressure was reduced to 200 mmHg with a vacuum pump and the solution was concentrated at about 65 ° C. for about 90 minutes to remove a predetermined amount of water, thereby obtaining a polymer aqueous solution (1) having a solid content concentration of 40%. The weight average molecular weight (Mw) of the polymer in the polymer aqueous solution (1) was 5,000.
次に、還流冷却管および攪拌機を備えた容量２ＬのＳＵＳ３１６製セパラブルフラスコに、イオン交換水５１３ｇと重合体水溶液（１）５２０ｇとを仕込み、攪拌下、室温にて２５％アンモニア水９８ｇを１５分間かけて滴下したのち、続いて、水酸化カルシウムの粉体５４ｇを３０分間かけて投入し、その後９０分間攪拌して、固形分濃度２０％の水溶液としてポリカルボン酸系重合体を得た。
得られたポリカルボン酸系重合体は、カルボキシル基含有不飽和単量体に由来する構成単位が有する全カルボキシル基のうちの５０モル％がカルシウムで中和され、５０モル％がアンモニアで中和されたものであり、その重量平均分子量（Ｍｗ）は６，０００であった。
Next, a SUS316 separable flask having a capacity of 2 L equipped with a reflux condenser and a stirrer was charged with 513 g of ion-exchanged water and 520 g of the aqueous polymer solution (1), and 15 g of 25% aqueous ammonia 98 g at room temperature with stirring. After dropwise addition over a period of 54 minutes, 54 g of calcium hydroxide powder was then added over 30 minutes, followed by stirring for 90 minutes to obtain a polycarboxylic acid polymer as an aqueous solution having a solid content concentration of 20%.
In the obtained polycarboxylic acid-based polymer, 50 mol% of all the carboxyl groups in the structural unit derived from the carboxyl group-containing unsaturated monomer is neutralized with calcium, and 50 mol% is neutralized with ammonia. The weight average molecular weight (Mw) was 6,000.
〔実施例２〕
実施例１におけるイオン交換水の仕込み量と８０％ＡＡおよび１５％ＡＰＳの使用量をそれぞれ、イオン交換水の仕込量は２８００ｇ、８０％ＡＡの使用量は６３０ｇ（アクリル酸７モル）、１５％ＡＰＳの使用量は１８６．７ｇ（アクリル酸１モルに対して過硫酸アンモニウム４ｇ）に変更したこと以外は、実施例１と同様にして、固形分濃度４０％の重合体水溶液（２）を得た。該重合体水溶液（２）中のポリマーの重量平均分子量（Ｍｗ）は１０，０００であった。
次に、重合体水溶液（１）の代わりに重合体水溶液（２）を用いたこと以外は、実施例１と同様にして、固形分濃度２０％の水溶液としてポリカルボン酸系重合体を得た。
[Example 2]
The amount of ion-exchanged water and the amount of 80% AA and 15% APS used in Example 1 were 2800 g, the amount of 80% AA used was 630 g (acrylic acid 7 mol) and 15%, respectively. A polymer aqueous solution (2) having a solid content concentration of 40% was obtained in the same manner as in Example 1 except that the amount of APS used was changed to 186.7 g (4 g of ammonium persulfate per 1 mol of acrylic acid). . The weight average molecular weight (Mw) of the polymer in the polymer aqueous solution (2) was 10,000.
Next, a polycarboxylic acid polymer was obtained as an aqueous solution having a solid content concentration of 20% in the same manner as in Example 1 except that the polymer aqueous solution (2) was used instead of the polymer aqueous solution (1). .
得られたポリカルボン酸系重合体は、カルボキシル基含有不飽和単量体に由来する構成単位が有する全カルボキシル基のうちの５０モル％がカルシウムで中和され、５０モル％がアンモニアで中和されたものであり、その重量平均分子量（Ｍｗ）は１２，０００であった。
〔実施例２−Ｉ〕
実施例２で得られた固形分濃度２０％のポリカルボン酸系重合体水溶液を用い、下記の配合で塗料化（各成分を混合）したのち、固形分濃度２０％になるように水で希釈して、水性シーラーを得た。
In the obtained polycarboxylic acid-based polymer, 50 mol% of all the carboxyl groups in the structural unit derived from the carboxyl group-containing unsaturated monomer is neutralized with calcium, and 50 mol% is neutralized with ammonia. The weight average molecular weight (Mw) was 12,000.
[Example 2-I]
Using the polycarboxylic acid polymer aqueous solution with a solid content concentration of 20% obtained in Example 2, after coating with the following composition (mixing each component), diluted with water to a solid content concentration of 20% An aqueous sealer was obtained.
実施例２のポリカルボン酸系重合体水溶液：３００ｇ
分散剤（花王社製「デモールＥＰ」）：２０．０ｇ
消泡剤（サンノプコ社製「ノプコ８０３４」）：０．３ｇ
ルチル型酸化チタン（石原産業社製「Ｒ−７８０」）３０．０ｇ
炭酸カルシウム（日東粉化社製「ＮＳ−１００」）：１５ｇ
カオリン（山陽クレー社製「ＡＡカオリン」）：１５ｇ
増粘剤（旭電化社製「アデカノールＵＨ４２０」の５％水溶液）：１．０ｇ
〔実施例３〕
還流冷却管および攪拌機を備えた容量２ＬのＳＵＳ３１６製セパラブルフラスコに、イオン交換水４９５ｇと、実施例１と同様にして得た重合体水溶液（１）５２０ｇとを仕込み、攪拌下、室温にて２５％アンモニア水９８ｇを１５分間かけて滴下したのち、続いて、水酸化カルシウムの粉体３２ｇを３０分間かけて投入し、さらに続いて、水酸化マグネシウムの粉体１７ｇを３０分間かけて投入し、その後９０分間攪拌して、固形分濃度２０％の水溶液としてポリカルボン酸系重合体を得た。
Polycarboxylic acid polymer aqueous solution of Example 2: 300 g
Dispersant (“Demol EP” manufactured by Kao Corporation): 20.0 g
Antifoaming agent (San Nopco “Nopco 8034”): 0.3 g
Rutile type titanium oxide (Ishihara Sangyo "R-780") 30.0g
Calcium carbonate (“NS-100” manufactured by Nitto Flour Chemical Co., Ltd.): 15 g
Kaolin ("AA Kaolin" manufactured by Sanyo Clay): 15g
Thickener (5% aqueous solution of “Adecanol UH420” manufactured by Asahi Denka Co., Ltd.): 1.0 g
Example 3
A SUS316 separable flask having a capacity of 2 L equipped with a reflux condenser and a stirrer was charged with 495 g of ion-exchanged water and 520 g of a polymer aqueous solution (1) obtained in the same manner as in Example 1, and the mixture was stirred at room temperature. After dropping 98 g of 25% aqueous ammonia over 15 minutes, 32 g of calcium hydroxide powder was added over 30 minutes, and then 17 g of magnesium hydroxide powder was added over 30 minutes. Then, the mixture was stirred for 90 minutes to obtain a polycarboxylic acid polymer as an aqueous solution having a solid content concentration of 20%.
得られたポリカルボン酸系重合体は、カルボキシル基含有不飽和単量体に由来する構成単位が有する全カルボキシル基のうちの３０モル％がカルシウムで中和され、２０モル％がマグネシウムで中和され、５０モル％がアンモニアで中和されたものであり、その重量平均分子量（Ｍｗ）は１２，０００であった。
〔比較例１〕
実施例２で得られた重合体水溶液（２）を、固形分濃度２０％になるように水で希釈し、これを比較用のポリカルボン酸系重合体の水溶液とした。
得られたポリカルボン酸系重合体は、カルボキシル基含有不飽和単量体に由来する構成単位が有する全カルボキシル基のうちの１００モル％が中和されていないものであり、その重量平均分子量（Ｍｗ）は１０，０００であった。
In the obtained polycarboxylic acid-based polymer, 30 mol% of all the carboxyl groups of the structural unit derived from the carboxyl group-containing unsaturated monomer is neutralized with calcium, and 20 mol% is neutralized with magnesium. 50 mol% was neutralized with ammonia, and its weight average molecular weight (Mw) was 12,000.
[Comparative Example 1]
The aqueous polymer solution (2) obtained in Example 2 was diluted with water so that the solid concentration was 20%, and this was used as an aqueous solution of a polycarboxylic acid polymer for comparison.
The obtained polycarboxylic acid-based polymer is one in which 100 mol% of all carboxyl groups in the structural unit derived from the carboxyl group-containing unsaturated monomer is not neutralized, and its weight average molecular weight ( Mw) was 10,000.
〔比較例２〕
還流冷却管および攪拌機を備えた容量２ＬのＳＵＳ３１６製セパラブルフラスコに、イオン交換水３２５ｇと、実施例２と同様にして得た重合体水溶液（２）５２０ｇとを仕込み、攪拌下、室温にて２５％アンモニア水１９７ｇを３０分間かけて滴下して、固形分濃度２０％の水溶液として比較用のポリカルボン酸系重合体を得た。
得られたポリカルボン酸系重合体は、カルボキシル基含有不飽和単量体に由来する構成単位が有する全カルボキシル基のうちの１００モル％がアンモニアで中和されたものであり、その重量平均分子量（Ｍｗ）は１０，０００であった。
[Comparative Example 2]
A SUS316 separable flask having a capacity of 2 L equipped with a reflux condenser and a stirrer was charged with 325 g of ion-exchanged water and 520 g of a polymer aqueous solution (2) obtained in the same manner as in Example 2, and the mixture was stirred at room temperature. 197 g of 25% aqueous ammonia was added dropwise over 30 minutes to obtain a polycarboxylic acid polymer for comparison as an aqueous solution having a solid concentration of 20%.
The obtained polycarboxylic acid-based polymer is obtained by neutralizing 100 mol% of all carboxyl groups of the structural unit derived from the carboxyl group-containing unsaturated monomer with ammonia, and its weight average molecular weight (Mw) was 10,000.
以上の実施例１〜３および比較例１、２で得られたポリカルボン酸系重合体の水溶液をそのまま水性シーラーとし、実施例２−Ｉで得られた水性シーラーとともに、以下の評価を行った。すなわち、珪酸カルシウム板（Ａ＆Ａマテリアル製「ハイラック０．８軽質ケイカル」：ＪＩＳ−Ａ５４０３、表中では「珪カル」と略す）を基材とし、各水性シーラー（いずれも固形分濃度２０％）を、あらかじめ５５℃になるようにプレヒートしておいた前記基材にエアレススプレーにて塗布量８０ｇ／ｍ２（ｗｅｔ）になるように塗布したのち、１２０℃で５分間乾燥して、試験体を作製した。そして、下記の方法にて得られた試験体の含浸密着性および耐水性を評価した。なお、実施例２で得られたポリカルボン酸系重合体の水溶液を水性シーラーとしたものについては、別途、基材としてスレート板（ノザワ社製「ノザワフレキシブルシート」：ＪＩＳ−Ａ５４０３、表中では「スレート板」と略す）を用いた試験体を作製し（作製方法は、基材を変更したこと以外、前述と同様の方法とした。）、該スレート板を基材とした試験体についても同様の評価を行った。結果を表１に示す。 The aqueous solutions of the polycarboxylic acid polymers obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were directly used as an aqueous sealer, and the following evaluation was performed together with the aqueous sealer obtained in Example 2-I. . That is, a calcium silicate plate (“Hilac 0.8 light calcium” manufactured by A & A Materials: JIS-A5403, abbreviated as “silical” in the table) is used as a base material, and each aqueous sealer (all solid content concentration is 20%). Was applied to the base material that had been preheated to 55 ° C. by airless spraying so that the application amount would be 80 g / m 2 (wet), and then dried at 120 ° C. for 5 minutes. Was made. And the impregnation adhesiveness and water resistance of the test body obtained by the following method were evaluated. In addition, about what used the aqueous solution of the polycarboxylic acid-type polymer obtained in Example 2 as the aqueous sealer, a slate plate (“Nozawa Flexible Sheet” manufactured by Nozawa Co., Ltd .: JIS-A5403, in the table) (Abbreviated as “slate plate”) was prepared (the preparation method was the same as described above except that the base material was changed), and the test body using the slate plate as a base material was also used. Similar evaluations were made. The results are shown in Table 1.
＜含浸密着性＞
試験体の塗膜面にカッターナイフを用いて２ｍｍ間隔で３６マスの碁盤目の切込みを入れ、該切り込みを入れた塗膜面に布粘着テープ（菊水テープ（株）製「Ｎｏ．９１６」）を貼り、布粘着テープの上から消しゴムを２０回往復させて擦ることにより圧着させてから１分後に布粘着テープを垂直方向へ一気に引き剥がしたときの塗膜の剥離状態を調べ、下記の基準で評価した。
○：０〜４マス剥離した
△：５〜９マス剥離した
×：１０マス以上剥離した
＜耐水性＞
試験体を６０℃の温水に５日間浸漬し、その後２日間室温に放置することで乾燥させて得られた試験体を用いて、上記含浸密着性と同様の方法で評価した。
<Impregnation adhesion>
Using a cutter knife on the coating surface of the test specimen, a grid cut of 36 squares was made at intervals of 2 mm, and a cloth adhesive tape (“No. 916” manufactured by Kikusui Tape Co., Ltd.) was applied to the coating surface on which the cut was made. 1 minute after the pressure-sensitive adhesive was rubbed by reciprocating 20 times on and off the cloth adhesive tape, and the cloth adhesive tape was peeled off at once in a vertical direction. It was evaluated with.
○: 0 to 4 cells peeled Δ: 5 to 9 cells peeled ×: 10 cells or more peeled <Water resistance>
The test specimen was immersed in warm water at 60 ° C. for 5 days and then left to stand at room temperature for 2 days. The test specimen obtained by drying was evaluated in the same manner as the impregnation adhesion.
本発明にかかるポリカルボン酸系重合体は、例えば、洗剤ビルダー、スケール防止剤、キレート剤、セメント減水剤、インキ用バインダー、フィルム成形品、パルプ成形品、シート成形品、ラミネート用材料、例えば、車両用、プラスチック成形品用、家電品用、鋼製品、大型構造物、航空機用、建材用、建築用、瓦用、木工用などの上塗りもしくは中塗り水性塗料や水性シーラー等に有用であり、特に、水性シーラーの成分として用いた場合、コンクリートや無機質建材等の基材に対する含浸密着性に優れ、かつ、長期間使用しても再溶出したり剥がれたりせず良好な耐水性を発揮する水性シーラーを得させることのできるため、特に好ましい。 The polycarboxylic acid polymer according to the present invention is, for example, detergent builder, scale inhibitor, chelating agent, cement water reducing agent, ink binder, film molded product, pulp molded product, sheet molded product, laminating material, for example, Useful for overcoating or intermediate coating water-based paints, water-based sealers, etc. for vehicles, plastic molded products, home appliances, steel products, large structures, aircraft, building materials, construction, tiles, woodwork, etc. In particular, when used as a component of an aqueous sealer, it has excellent impregnation adhesion to substrates such as concrete and inorganic building materials, and exhibits good water resistance without re-elution or peeling even after long-term use. Since a sealer can be obtained, it is particularly preferable.
本発明にかかる水性シーラーは、基材に対する含浸密着性に優れ、かつ、長期間使用しても再溶出したり剥がれたりせず良好な耐水性を発揮し得るシーラーとして、コンクリート、オートクレーブ養生や水蒸気養生にて硬化させる無機質建材、瓦等の基材に好適に用いることができる。 The water-based sealer according to the present invention is excellent in impregnation adhesion to a substrate, and as a sealer that can exhibit good water resistance without re-elution or peeling even after long-term use, concrete, autoclave curing and water vapor It can be suitably used for base materials such as inorganic building materials and roof tiles to be cured by curing.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004162089A JP4451216B2 (en) | 2004-05-31 | 2004-05-31 | Water based sealer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004162089A JP4451216B2 (en) | 2004-05-31 | 2004-05-31 | Water based sealer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005343923A JP2005343923A (en) | 2005-12-15 |
| JP4451216B2 true JP4451216B2 (en) | 2010-04-14 |
Family
ID=35496607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004162089A Expired - Lifetime JP4451216B2 (en) | 2004-05-31 | 2004-05-31 | Water based sealer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4451216B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7879406B2 (en) | 2006-05-15 | 2011-02-01 | Harris Research, Inc | Sealer composition |
| JP5371028B2 (en) * | 2008-03-31 | 2013-12-18 | 株式会社日本触媒 | Method for producing (meth) acrylic acid polymer |
| JP6621250B2 (en) * | 2015-06-02 | 2019-12-18 | 株式会社日本触媒 | Polycarboxylic acid polymer aqueous solution and method for producing the same |
-
2004
- 2004-05-31 JP JP2004162089A patent/JP4451216B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005343923A (en) | 2005-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2015139467A1 (en) | Amphoteric betaine-type polycarboxylic acid water reducer and preparation method therefor | |
| EP2518116B1 (en) | Aqueous compositions comprising ion exchange resins that deliver paint and primer properties in a coating | |
| RU2602889C2 (en) | Stabilized aqueous compositions containing cationic polymers providing coating with properties of paint and primer | |
| WO2013119521A1 (en) | Latex binders useful in zero or low voc coating compositions | |
| CN107849186A (en) | Coating additive | |
| CN103509419A (en) | Wood protection paints | |
| JP4451216B2 (en) | Water based sealer | |
| JP2006151703A (en) | Polymer cement composition for water proofing and hardened article thereof, and method of producing the same | |
| CN105860723B (en) | Environment-friendlywater-based water-based paint and preparation method thereof | |
| JP2011072851A (en) | Scale inhibitor containing amino group-containing copolymer | |
| JP6298646B2 (en) | Carboxyl group-containing copolymer | |
| EP1197502B1 (en) | Waterborne resin emulsion and waterborne coating | |
| JPS58198513A (en) | Production of aqueous dispersion composition | |
| TWI294887B (en) | ||
| WO2022153867A1 (en) | (meth)acrylic acid copolymer | |
| JP5727717B2 (en) | Method for producing polymer emulsion | |
| JP5219773B2 (en) | Aqueous resin dispersion for coating inorganic substrates | |
| JPH02151669A (en) | Coating composition | |
| WO2017122700A1 (en) | Aqueous dispersion, production process therefor, water-based coating material, and coated article | |
| JP2017170395A (en) | Silica scale inhibitor and inhibiting method | |
| CN103890022B (en) | Isoprene alcohol, monoene belong to unsaturated monocarboxylic acid and the copolymer of sulfonic acid and production method thereof and purposes | |
| WO2016152450A1 (en) | Copolymer | |
| JPH04164907A (en) | Aqueous fluororesin dispersion, its production, resin composition containing the dispersion, and article coated with the same composition | |
| JP6431405B2 (en) | Method for preventing coloring of aqueous solution of polycarboxylic acid polymer | |
| CN109294364A (en) | A kind of anticorrosion water-soluble coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070112 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090828 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090924 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091124 |
|
| 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: 20100126 |
|
| 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: 20100127 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4451216 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130205 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140205 Year of fee payment: 4 |