JP2007254632A - Acrylic resin and composition comprising the same - Google Patents
Acrylic resin and composition comprising the same Download PDFInfo
- Publication number
- JP2007254632A JP2007254632A JP2006082363A JP2006082363A JP2007254632A JP 2007254632 A JP2007254632 A JP 2007254632A JP 2006082363 A JP2006082363 A JP 2006082363A JP 2006082363 A JP2006082363 A JP 2006082363A JP 2007254632 A JP2007254632 A JP 2007254632A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- acrylic resin
- meth
- double bond
- weight
- 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.)
- Granted
Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 81
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- -1 alkyl acrylic ester Chemical class 0.000 claims abstract description 77
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims description 8
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 8
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 22
- 229920005989 resin Polymers 0.000 abstract description 22
- 238000006116 polymerization reaction Methods 0.000 abstract description 16
- 230000001846 repelling effect Effects 0.000 abstract description 7
- 238000004078 waterproofing Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 23
- 230000035699 permeability Effects 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 16
- 239000003995 emulsifying agent Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000011342 resin composition Substances 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000012085 test solution Substances 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000002518 antifoaming agent Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 5
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 230000003449 preventive effect Effects 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000004 White lead Inorganic materials 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 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 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-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
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- CHPNMYQJQQGAJS-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C(C)=C CHPNMYQJQQGAJS-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- JZYAVTAENNQGJB-UHFFFAOYSA-N 3-tripropoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C(C)=C JZYAVTAENNQGJB-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- XKTMIJODWOEBKO-UHFFFAOYSA-M Guinee green B Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC=CC=2)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 XKTMIJODWOEBKO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 241001147388 Uncia Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- PRSMTOHTFYVJSQ-UHFFFAOYSA-N [Ca].[Pb] Chemical compound [Ca].[Pb] PRSMTOHTFYVJSQ-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 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
- 239000006229 carbon black Substances 0.000 description 1
- GTLQZNKUEFUUIS-UHFFFAOYSA-N carbonic acid;cyclohexanamine Chemical compound OC(O)=O.NC1CCCCC1 GTLQZNKUEFUUIS-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- QTBWAKWPKYZSRL-UHFFFAOYSA-N ethenol;phenol Chemical group OC=C.OC1=CC=CC=C1 QTBWAKWPKYZSRL-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000000693 micelle Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- PYUYQYBDJFMFTH-WMMMYUQOSA-N naphthol red Chemical compound CCOC1=CC=CC=C1NC(=O)C(C1=O)=CC2=CC=CC=C2\C1=N\NC1=CC=C(C(N)=O)C=C1 PYUYQYBDJFMFTH-WMMMYUQOSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- PJQYNUFEEZFYIS-UHFFFAOYSA-N perylene maroon Chemical compound C=12C3=CC=C(C(N(C)C4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)N(C)C(=O)C4=CC=C3C1=C42 PJQYNUFEEZFYIS-UHFFFAOYSA-N 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
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 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
- 239000000843 powder Substances 0.000 description 1
- NOBSUVLSUXZMQP-UHFFFAOYSA-N prop-2-enyl(dipropoxy)silane Chemical compound CCCO[SiH](CC=C)OCCC NOBSUVLSUXZMQP-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000011041 water permeability test Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
本発明はアクリル系樹脂及びそれを含む組成物に関するものであり、特に無機質成形部材のシーラーとして利用されるアクリル系樹脂及びそれを含む組成物に関する。 The present invention relates to an acrylic resin and a composition containing the same, and more particularly to an acrylic resin used as a sealer for an inorganic molded member and a composition containing the same.
各種基材（建築材料や紙等）に防湿性を付与する方法として、防湿性を有するフィルム及びコーティング材を利用する方法が知られている。フィルムを基材に貼付すると、操作が煩雑で人件費及び材料費等がかかる。また、コーティング材として、合成樹脂に塩素化パラフィン樹脂を混合した樹脂組成物が提案されているが、塩素系化合物を含むので、環境面で好ましくない。 As a method for imparting moisture resistance to various base materials (such as building materials and paper), a method using a moisture-proof film and a coating material is known. When a film is attached to a base material, the operation is complicated and labor costs and material costs are required. Moreover, although the resin composition which mixed the chlorinated paraffin resin with the synthetic resin as a coating material is proposed, since a chlorine type compound is included, it is unpreferable on an environmental viewpoint.
このような課題を解決するため、ワックスの水分散体にアクリルエマルジョン又はゴム系ラテックスを混合する方法が既知である。例えば、特許文献１は、水性アクリル樹脂にワックス系エマルジョンを添加することで防水性、防湿性に優れた塗料用樹脂が得られることを開示する。しかし、この塗料用樹脂を基材に塗工し、さらに、上塗り剤を重ね塗りすると、上塗り剤がこの塗料用樹脂にはじかれる傾向を有する。塗料用樹脂を塗工して乾燥する時に、防湿成分であるワックスが塗料用樹脂表面にブリードアウトした結果、このワックスによって上塗り剤がはじかれるから、このような現象が生ずると考えられる。 In order to solve such a problem, a method of mixing an acrylic emulsion or rubber latex with an aqueous dispersion of wax is known. For example, Patent Document 1 discloses that a coating resin having excellent waterproofness and moisture resistance can be obtained by adding a wax-based emulsion to an aqueous acrylic resin. However, when this coating resin is applied to a substrate and the overcoat is further applied, the topcoat tends to be repelled by the coating resin. When the coating resin is applied and dried, the wax, which is a moisture-proof component, bleeds out on the surface of the coating resin, so that the top coat is repelled by the wax, and this phenomenon is considered to occur.
また、特許文献２には、ステアリル（メタ）アクリレート（そのアルキル基の炭素数は１８である）を用いることで、防湿性能がより向上した防湿剤が記載されている。しかしながら、炭素数が１８のステアリル基を有する（メタ）アクリレートは重合性が不十分なので、特許文献２の段落番号００１５〜００１８に記載されているような、特殊な分散剤が必要となる。更に、この特殊な分散剤は、水溶性成分であるカルボキシル基を多く含み、分子量も低いので、この特殊な分散剤を樹脂に配合すると、樹脂の耐水性が低下し、樹脂の製造コストも高くなる。更に、本発明者の検討によると、後に比較例４で示すように、ステアリル（メタ）アクリレートを用いると、良好な基材密着性を得られないことも明らかとなった。 Patent Document 2 describes a moisture-proofing agent that has further improved moisture-proof performance by using stearyl (meth) acrylate (the alkyl group of which has 18 carbon atoms). However, since the (meth) acrylate having a stearyl group having 18 carbon atoms has insufficient polymerizability, a special dispersant as described in paragraph Nos. 0015 to 0018 of Patent Document 2 is required. Furthermore, this special dispersant contains many carboxyl groups, which are water-soluble components, and has a low molecular weight. Therefore, when this special dispersant is added to the resin, the water resistance of the resin is lowered and the production cost of the resin is high. Become. Further, according to the study by the present inventor, as will be shown later in Comparative Example 4, it was also revealed that when stearyl (meth) acrylate was used, good substrate adhesion could not be obtained.
本発明は、以上のような課題を解決するためになされたものであり、環境面から好ましくない、防水性及び防湿性が不十分である、上塗り剤のハジキを生ずる、特許文献２に記載されたような特殊な分散剤を必要とし、容易に低コストな重合方法で製造できない、良好な基材密着性を得られないという課題の少なくとも一を緩和し、好ましくは実質的に解消するアクリル系樹脂及びその樹脂を含有する組成物を提供することである。 The present invention has been made in order to solve the above-described problems, and is described in Patent Document 2 which causes repelling of a top coating agent, which is not environmentally preferable, has insufficient waterproofness and moisture-proofing properties, and the like. An acrylic system that alleviates, preferably substantially eliminates, at least one of the problems of requiring a special dispersant as described above, which cannot be easily produced by a low-cost polymerization method, and cannot obtain good substrate adhesion It is to provide a resin and a composition containing the resin.
本発明者らは、かかる課題を解決するために鋭意検討を重ねた結果、アクリル系樹脂を含む防湿樹脂組成物を製造する場合、（Ａ）アルキル基が特定の範囲の炭素数を有するアルキル（メタ）アクリル酸エステルと、スチレン系誘導体及びアルキル基が比較的少ない炭素数を有するアルキル（メタ）アクリル酸エステルを含む（Ｂ）エチレン性二重結合を有する単量体を、特定の重量比で、共重合することで得られるアクリル系樹脂が、上述の課題を解決することができることを見出して、本発明を完成することに至ったものである。 As a result of intensive studies in order to solve such problems, the present inventors have produced (A) an alkyl group in which an alkyl group has a specific number of carbon atoms (A) when producing a moisture-proof resin composition containing an acrylic resin ( (B) monomer having an ethylenic double bond including a (meth) acrylic acid ester and an alkyl (meth) acrylic acid ester having a styrene derivative and an alkyl group having a relatively small number of carbon atoms in a specific weight ratio. The inventors have found that an acrylic resin obtained by copolymerization can solve the above-mentioned problems, and have completed the present invention.
即ち、本発明は、一の要旨において、新たなアクリル系樹脂を提供し、それは、
（Ａ）アルキル（メタ）アクリル酸エステル：０．５〜２４重量部と、
（Ｂ）エチレン性二重結合を有する単量体：７６〜９９．５重量部とを、
共重合することで得られるアクリル系樹脂であって、
（Ａ）アルキル（メタ）アクリル酸エステルは、
（ａ１）アルキル基の炭素数が１０〜１６であるアルキルアクリル酸エステル及び
（ａ２）アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステル
から選択される少なくとも１種であり（以下、（Ａ）の有するアルキル基を「長鎖アルキル基」ともいう）、
（Ｂ）エチレン性二重結合を有する単量体は、
（ｂ１）スチレン系誘導体及び
（ｂ２）アルキル基の炭素数が８以下であるアルキル（メタ）アクリル酸エステル
を含む。このアクリル樹脂は、防湿性を有する防湿アクリル樹脂として好適に使用することができる。
That is, the present invention provides, in one aspect, a new acrylic resin,
(A) alkyl (meth) acrylic acid ester: 0.5 to 24 parts by weight;
(B) Monomer having an ethylenic double bond: 76-99.5 parts by weight
An acrylic resin obtained by copolymerization,
(A) Alkyl (meth) acrylic acid ester is
(A1) at least one selected from alkyl acrylates having 10 to 16 carbon atoms in the alkyl group and (a2) alkyl methacrylates having 14 to 16 carbon atoms in the alkyl group (hereinafter referred to as ( The alkyl group of A) is also referred to as a “long-chain alkyl group”),
(B) The monomer having an ethylenic double bond is
(B1) a styrene derivative and (b2) an alkyl (meth) acrylic acid ester having 8 or less carbon atoms in the alkyl group. This acrylic resin can be suitably used as a moisture-proof acrylic resin having moisture resistance.
本発明の一の態様において、
（ａ１）アルキル基の炭素数が１０〜１６であるアルキルアクリル酸エステルは、ラウリルアクリレートであり、
（ａ２）アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステルは、セチルメタクリレートであるアクリル系樹脂を提供する。
In one aspect of the invention,
(A1) The alkyl acrylate ester having 10 to 16 carbon atoms in the alkyl group is lauryl acrylate,
(A2) The alkyl methacrylate having 14 to 16 carbon atoms in the alkyl group provides an acrylic resin that is cetyl methacrylate.
本発明の他の態様において、（Ｂ）エチレン性二重結合を有する単量体は、さらに、（ｂ３）エチレン性二重結合を有するアルコキシシランを含むアクリル系樹脂を提供する。
本発明の好ましい態様において、（Ａ）アルキル（メタ）アクリル酸エステルと（Ｂ）エチレン性二重結合を有する単量体との総和を１００重量部として、（Ｂ）エチレン性二重結合を有する単量体は、（ｂ３）エチレン性二重結合を有するアルコキシシランを０．０１〜５．０重量部含有するアクリル系樹脂を提供する。
本発明の更に好ましい態様において、共重合を乳化重合で行うアクリル系樹脂を提供する。
In another aspect of the present invention, the monomer (B) having an ethylenic double bond further provides (b3) an acrylic resin containing an alkoxysilane having an ethylenic double bond.
In a preferred embodiment of the present invention, the total of (A) alkyl (meth) acrylate and (B) monomer having an ethylenic double bond is 100 parts by weight, and (B) has an ethylenic double bond. The monomer provides (b3) an acrylic resin containing 0.01 to 5.0 parts by weight of alkoxysilane having an ethylenic double bond.
In a further preferred embodiment of the present invention, there is provided an acrylic resin in which the copolymerization is carried out by emulsion polymerization.
本発明の他の要旨において、上述のアクリル系樹脂を含むアクリル系樹脂組成物を提供する。このアクリル系樹脂組成物は、防湿性を有する防湿アクリル系樹脂組成物として好適に使用することができる。
本発明の好ましい要旨において、無機質成形部材用シーラーとして用いられる上述のアクリル系樹脂組成物を提供する。
In another aspect of the present invention, an acrylic resin composition containing the above-described acrylic resin is provided. This acrylic resin composition can be suitably used as a moisture-proof acrylic resin composition having moisture resistance.
The preferable gist of the present invention provides the above-mentioned acrylic resin composition used as a sealer for an inorganic molded member.
本発明のアクリル系樹脂は、
（Ａ）アルキル（メタ）アクリル酸エステル：０．５〜２４重量部と、
（Ｂ）エチレン性二重結合を有する単量体：７６〜９９．５重量部とを、
共重合することで得られるアクリル系樹脂であって、
（Ａ）アルキル（メタ）アクリル酸エステルは、
（ａ１）アルキル基の炭素数が１０〜１６であるアルキルアクリル酸エステル及び
（ａ２）アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステル
から選択される少なくとも１種であり、
（Ｂ）エチレン性二重結合を有する単量体は、
（ｂ１）スチレン系誘導体及び
（ｂ２）アルキル基の炭素数が８以下であるアルキル（メタ）アクリル酸エステル
を含み、
アルキル基の炭素数が１８以上であるアルキル（メタ）アクリル酸エステルを含むものではない。即ち、（Ａ）アルキル（メタ）アクリル酸エステル及び（Ｂ）エチレン性二重結合を有する単量体の双方は、重合性を低下させるほど鎖長が長いアルキル基を有するモノマーを含むものではないので、それらを共重合するために特許文献２に記載の特殊な重合用分散剤を必要とするものでもない。更に、アルキル基の炭素数が１８以上であるアルキル（メタ）アクリル酸エステルを含むものではないので、基材密着性も更に向上され得る。
The acrylic resin of the present invention is
(A) alkyl (meth) acrylic acid ester: 0.5 to 24 parts by weight;
(B) Monomer having an ethylenic double bond: 76-99.5 parts by weight
An acrylic resin obtained by copolymerization,
(A) Alkyl (meth) acrylic acid ester is
(A1) at least one selected from alkyl acrylates having 10 to 16 carbon atoms in the alkyl group and (a2) alkyl methacrylates having 14 to 16 carbon atoms in the alkyl group,
(B) The monomer having an ethylenic double bond is
(B1) a styrenic derivative and (b2) an alkyl (meth) acrylic acid ester having 8 or less carbon atoms in the alkyl group,
It does not include an alkyl (meth) acrylic ester in which the alkyl group has 18 or more carbon atoms. That is, both (A) the alkyl (meth) acrylate and (B) the monomer having an ethylenic double bond do not include a monomer having an alkyl group with a long chain length so as to reduce the polymerizability. Therefore, it does not require a special polymerization dispersant described in Patent Document 2 in order to copolymerize them. Furthermore, since it does not contain an alkyl (meth) acrylic acid ester having 18 or more carbon atoms in the alkyl group, the substrate adhesion can be further improved.
これに対し、特許文献２に記載の防湿剤は、（メタ）アクリル酸ステアリルを必須成分として含み、特許文献２の段落番号００１５に記載されるように、特殊な重合用分散剤も必須成分として含むことが必要である。このように特許文献２に記載の防湿剤は、（メタ）アクリル酸ステアリルを必須成分として含み、かつ、特殊な重合用分散剤を重合するために必要とするので、本発明に係るアクリル系樹脂と特許文献２に記載の防湿剤とは異なるものである。
従って、本発明のアクリル系樹脂は、環境面から好ましくない、防水性及び防湿性が不十分である、上塗り剤のハジキを生ずる、特許文献２に記載されたような特殊な分散剤を必要とし、容易に低コストな重合方法で製造できない、良好な基材密着性を得られないという課題の少なくとも一を緩和し、好ましくは実質的に解消することができる。
On the other hand, the moisture-proofing agent described in Patent Document 2 contains stearyl (meth) acrylate as an essential component. As described in Paragraph No. 0015 of Patent Document 2, a special polymerization dispersant is also included as an essential component. It is necessary to include. As described above, since the moisture-proofing agent described in Patent Document 2 contains stearyl (meth) acrylate as an essential component and is necessary for polymerizing a special polymerization dispersant, the acrylic resin according to the present invention is used. And the moisture-proofing agent described in Patent Document 2 are different.
Therefore, the acrylic resin of the present invention requires a special dispersant as described in Patent Document 2, which is undesirable from the environmental viewpoint, has insufficient waterproofness and moisture resistance, and causes repelling of the top coat. At least one of the problems that it cannot be easily produced by a low-cost polymerization method and good substrate adhesion cannot be obtained can be mitigated, and preferably substantially eliminated.
本発明のアクリル系樹脂は、
（ａ１）アルキル基の炭素数が１０〜１６であるアルキルアクリル酸エステルは、ラウリルアクリレートであり、
（ａ２）アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステルは、セチルメタクリレートである請求項１に記載のアクリル系樹脂の場合、
より防水性及び防湿性が向上される。
The acrylic resin of the present invention is
(A1) The alkyl acrylate ester having 10 to 16 carbon atoms in the alkyl group is lauryl acrylate,
(A2) The alkyl methacrylate having 14 to 16 carbon atoms in the alkyl group is cetyl methacrylate. In the case of the acrylic resin according to claim 1,
Water resistance and moisture resistance are further improved.
本発明のアクリル系樹脂は、
（Ｂ）エチレン性二重結合を有する単量体は、さらに、（ｂ３）エチレン性二重結合を有するアルコキシシランを含む場合、より基材密着性が向上する。
The acrylic resin of the present invention is
When the monomer (B) having an ethylenic double bond further contains (b3) an alkoxysilane having an ethylenic double bond, the substrate adhesion is further improved.
（Ａ）アルキル（メタ）アクリル酸エステルと（Ｂ）エチレン性二重結合を有する単量体との総和を１００重量部として、（Ｂ）エチレン性二重結合を有する単量体は、（ｂ３）エチレン性二重結合を有するアルコキシシランを０．０１〜５．０重量部含有する場合、重合性を損なうことなく、より基材密着性を向上することができる。
本発明のアクリル系樹脂は、共重合を乳化重合で行う場合、より高分子量化が可能となり、防水性及び防湿性が向上する。
The total of (A) alkyl (meth) acrylate and (B) monomer having an ethylenic double bond is 100 parts by weight, and (B) the monomer having an ethylenic double bond is (b3 ) In the case where 0.01 to 5.0 parts by weight of alkoxysilane having an ethylenic double bond is contained, the substrate adhesion can be further improved without impairing the polymerizability.
In the acrylic resin of the present invention, when copolymerization is carried out by emulsion polymerization, higher molecular weight is possible, and waterproofness and moisture resistance are improved.
本発明のアクリル系樹脂組成物は、上述の本発明のアクリル系樹脂を含むので、環境面から好ましくない、防水性及び防湿性が不十分である、上塗り剤のハジキを生ずる、特許文献２に記載されたような特殊な分散剤を必要とし、容易に低コストな重合方法で製造できない、良好な基材密着性を得られないという課題の少なくとも一を緩和し、好ましくは実質的に解消することができる。
更に、本発明のアクリル系樹脂組成物は、上述の本発明のアクリル系樹脂を含んで成るので、無機質成形部材用シーラーとして好適に用いることができる。
Since the acrylic resin composition of the present invention contains the above-mentioned acrylic resin of the present invention, it is undesirable from the viewpoint of the environment. Alleviates at least one of the problems of requiring a special dispersant as described, being not easily produced by a low-cost polymerization method, and not being able to obtain good substrate adhesion, and preferably substantially eliminated be able to.
Furthermore, since the acrylic resin composition of the present invention comprises the acrylic resin of the present invention described above, it can be suitably used as a sealer for inorganic molded members.
尚、本明細書において、「エチレン性二重結合」とは、ラジカル重合可能な炭素原子間二重結合をいう。そのようなエチレン性二重結合を有する官能基として、例えば、ビニル基（ＣＨ２＝ＣＨ−）、（メタ）アリル基（ＣＨ２＝ＣＨ−ＣＨ２−及びＣＨ２＝Ｃ（ＣＨ３）−ＣＨ２−）、（メタ）アクリロキシ基（ＣＨ２＝ＣＨ−ＣＯＯ−及びＣＨ２＝Ｃ（ＣＨ３）−ＣＯＯ−）、及び−ＣＯＯ−ＣＨ＝ＣＨ−ＣＯＯ−等を例示できる。「エチレン性二重結合を有する単量体」は、エチレン性二重結合を有する官能基を単独で又は組み合わせて有してよく、エチレン性二重結合を有する単量体の単独又は組み合わせであってよい。尚、本明細書においては、アクリル酸とメタクリル酸を総称して「（メタ）アクリル酸」ともいい、アクリル酸エステルとメタクリル酸エステルを総称して「（メタ）アクリル酸エステル」又は「（メタ）アクリレート」ともいう。その他も同様である。 In the present specification, “ethylenic double bond” refers to a double bond between carbon atoms capable of radical polymerization. Examples of such a functional group having an ethylenic double bond include a vinyl group (CH 2 ═CH—), a (meth) allyl group (CH 2 ═CH—CH 2 — and CH 2 ═C (CH 3 ) — CH 2 -), it can be exemplified (meth) acryloxy group (CH 2 = CH-COO- and CH 2 = C (CH 3) -COO-), and -COO-CH = CH-COO-, and the like. The “monomer having an ethylenic double bond” may have a functional group having an ethylenic double bond alone or in combination, and may be a monomer having an ethylenic double bond alone or in combination. It's okay. In this specification, acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”, and acrylic acid ester and methacrylic acid ester are collectively referred to as “(meth) acrylic acid ester” or “(meta ) Acrylate ". Others are the same.
本発明において、（Ａ）アルキル（メタ）アクリル酸エステルとは、（ａ１）アルキル基の炭素数が１０〜１６であるアルキルアクリル酸エステル及び（ａ２）アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステルから選択される少なくとも１種を意味する。アルキルアクリル酸エステルが有するアルキル基の炭素数が９以下の場合防湿性が劣り、炭素数が１６を超える場合重合性が低下し、共重合が困難と成り得るとともに良好な基材密着性を得られない。また、アルキルメタクリル酸エステルが有するアルキル基の炭素数が１３以下の場合樹脂の防湿性が劣り、炭素数が１６を超える場合樹脂を製造する際の重合性が低下して共重合が困難と成り得るとともに良好な基材密着性を得られない。 In the present invention, (A) an alkyl (meth) acrylate ester is (a1) an alkyl acrylate ester having 10 to 16 carbon atoms in the alkyl group and (a2) an alkyl group having 14 to 16 carbon atoms. It means at least one selected from alkyl methacrylates. When the carbon number of the alkyl group of the alkyl acrylate ester is 9 or less, the moisture resistance is inferior. When the carbon number exceeds 16, the polymerizability is lowered and the copolymerization may be difficult, and good substrate adhesion is obtained. I can't. Moreover, when the carbon number of the alkyl group which alkyl methacrylate has is 13 or less, the moisture resistance of the resin is inferior, and when the carbon number exceeds 16, the polymerizability at the time of producing the resin is lowered and the copolymerization becomes difficult. And good substrate adhesion cannot be obtained.
（ａ１）アルキル基の炭素数が１０〜１６であるアルキルアクリル酸エステルは、例えば炭素数が１０〜１６の長鎖アルキルアルコールとアクリル酸とをエステル化することにより得ることができ、そのような化合物としてより具体的には例えばデシルアクリレート、ラウリルアクリレート、ミリスチルアクリレート及びセチルアクリレート等を例示できる。アルキル基の炭素数が１０〜１６であるアルキルアクリル酸エステルとして、より防水性及び防湿性を向上することができるから、ラウリルアクリレートが特に好ましい。 (A1) The alkyl acrylate ester having 10 to 16 carbon atoms in the alkyl group can be obtained, for example, by esterifying a long-chain alkyl alcohol having 10 to 16 carbon atoms and acrylic acid. More specifically, examples of the compound include decyl acrylate, lauryl acrylate, myristyl acrylate and cetyl acrylate. As the alkyl acrylate ester having 10 to 16 carbon atoms in the alkyl group, lauryl acrylate is particularly preferable because it can further improve waterproofness and moisture resistance.
（ａ２）アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステルは、例えば炭素数が１４〜１６の長鎖アルキルアルコールとメタクリル酸とをエステル化することにより得ることができ、そのような化合物としてより具体的には例えばミリスチルメタクリレート及びセチルメタクリレートを例示できる。アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステルとして、これらの中でも、セチルメタクリレートが特に好ましい。
従って、（Ａ）アルキル（メタ）アクリル酸エステルは、ラウリルアクリレート及びセチルメタクリレートから選択される少なくとも一種であることが、より防水性及び防湿性を向上することができることから、特に好ましい。
(A2) An alkyl methacrylate having an alkyl group with 14 to 16 carbon atoms can be obtained, for example, by esterifying a long-chain alkyl alcohol having 14 to 16 carbon atoms with methacrylic acid. More specifically, examples of the compound include myristyl methacrylate and cetyl methacrylate. Of these, cetyl methacrylate is particularly preferable as the alkyl methacrylate having 14 to 16 carbon atoms in the alkyl group.
Therefore, the (A) alkyl (meth) acrylic acid ester is particularly preferably at least one selected from lauryl acrylate and cetyl methacrylate because the waterproofness and moisture resistance can be further improved.
本発明に係る（Ｂ）エチレン性二重結合を有する単量体は、上述のような「エチレン性二重結合」を有する単量体であって、更に（ｂ１）スチレン系誘導体及び（ｂ２）アルキル基の炭素数が８以下であるアルキル（メタ）アクリル酸エステルを含んで成る。
（ｂ１）スチレン系誘導体とは、スチレンに基づく誘導体を意味し、通常、スチレンの誘導体と認められるものが含まれる。本発明が目的とするアクリル系樹脂を得ることができるものであれば特に制限されるものではない。スチレン系誘導体として、例えばスチレン、ビニルトルエン、メチルスチレン等を例示できる。本発明では、スチレンが好ましい。
The monomer (B) having an ethylenic double bond according to the present invention is a monomer having an “ethylenic double bond” as described above, and (b1) a styrene derivative and (b2) It comprises an alkyl (meth) acrylic acid ester whose alkyl group has 8 or less carbon atoms.
(B1) The styrene derivative means a derivative based on styrene, and includes those that are generally recognized as derivatives of styrene. The present invention is not particularly limited as long as the intended acrylic resin can be obtained. Examples of the styrene derivative include styrene, vinyl toluene, and methyl styrene. In the present invention, styrene is preferred.
（ｂ２）アルキル基の炭素数が８以下であるアルキル（メタ）アクリル酸エステルは、例えば炭素数が８以下のアルキルアルコールと（メタ）アクリル酸とをエステル化することにより得ることができ、本発明が目的とするアクリル系樹脂を得ることができるものであれば特に制限されるものではない。そのような化合物としてより具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸オクチル等を例示できる。（尚、アルキル基は直鎖状でも、分枝状でも、環状でもよく、例えば、ヒドロキシル基等の置換基を有しても良い）。これらは単独で又は２種以上併せて用いることができる。 (B2) An alkyl (meth) acrylic acid ester having 8 or less carbon atoms in the alkyl group can be obtained by esterifying, for example, an alkyl alcohol having 8 or less carbon atoms and (meth) acrylic acid. The invention is not particularly limited as long as the intended acrylic resin can be obtained. More specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic. Examples include pentyl acid, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and the like. (Note that the alkyl group may be linear, branched or cyclic, and may have a substituent such as a hydroxyl group, for example). These may be used alone or in combination of two or more.
（Ｂ）エチレン性二重結合を有する単量体は、（ｂ３）エチレン性二重結合を有するアルコキシシランを更に含んでもよい。（ｂ３）エチレン性二重結合を有するアルコキシシランを更に含むことで、本発明に係る「アクリル系樹脂」は、基材密着性がより向上される。（ｂ３）「エチレン性二重結合を有するアルコキシシラン」とは、エチレン性二重結合を有し、少なくとも一のアルコキシ基を有するシランであって、本発明が目的とするアクリル樹脂を得ることができるものであれば特に制限されるものではない。そのようなエチレン性二重結合を有するアルコキシシランとして、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルメチルジエトキシシラン、ビニルメチルジプロポキシシラン、ビニルトリス（β-メトキシエトキシ）シラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルトリエトキシシラン、γ-メタクリロキシプロピルトリプロポキシシラン、γ-メタクリロキシプロピルメチルジメトキシシラン、γ-メタクリロキシプロピルトリス（イソプロポキシ）シラン等を例示できる。これらは単独でもしくは２種以上併せて用いることができる。エチレン性二重結合を有するアルコキシシランとして、エチレン性二重結合を有するジアルコキシシラン及びエチレン性二重結合を有するトリアルコキシシランが好ましく、エチレン性二重結合を有するトリアルコキシシランがより好ましく、γ-メタクリロキシプロピルトリメトキシシランが特に好ましい。 (B) The monomer having an ethylenic double bond may further contain (b3) an alkoxysilane having an ethylenic double bond. (B3) By further including an alkoxysilane having an ethylenic double bond, the “acrylic resin” according to the present invention is further improved in substrate adhesion. (B3) “Alkoxysilane having an ethylenic double bond” is a silane having an ethylenic double bond and having at least one alkoxy group, and the acrylic resin targeted by the present invention can be obtained. There is no particular limitation as long as it is possible. Examples of such alkoxysilane having an ethylenic double bond include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropoxysilane, and vinyltris. (Β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltripropoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltris (Isopropoxy) silane etc. can be illustrated. These may be used alone or in combination of two or more. As the alkoxysilane having an ethylenic double bond, a dialkoxysilane having an ethylenic double bond and a trialkoxysilane having an ethylenic double bond are preferable, a trialkoxysilane having an ethylenic double bond is more preferable, and γ -Methacryloxypropyltrimethoxysilane is particularly preferred.
（Ｂ）エチレン性二重結合を有する単量体は、本発明が目的とするアクリル系樹脂を得られる限り、上述した（Ａ）、（ｂ１）、（ｂ２）及び（ｂ３）以外の他の単量体を含んでいても良い。具体的には、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、無水マレイン酸等の（ｂ４）不飽和カルボン酸類；酢酸ビニル等のビニルエステル類；ビニルエーテル類；アクリロニトリル等のシアノ基含有単量体；アクリルアミド等の窒素含有単量体等；ジビニルベンゼン、ジアリルフタレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等の２〜３個の二重結合を有する単量体；グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシル（メタ）アクリレート、Ｎ−メチロールアクリルアミド、ジアセトンアクリルイアミド、アセトアセトキシエチル（メタ）アクリレート等の反応性単量体を含んでも良い。
（Ｂ）エチレン性二重結合を有する単量体は、上述の（ｂ４）不飽和カルボン酸類を含むことが好ましく、（ｂ４）不飽和カルボン酸を含むことで、重合性がより向上し得る。
(B) As long as the monomer having an ethylenic double bond can obtain the intended acrylic resin of the present invention, other than (A), (b1), (b2) and (b3) described above. A monomer may be included. Specifically, (b4) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and maleic anhydride; vinyl esters such as vinyl acetate; vinyl ethers; acrylonitrile, etc. Cyano group-containing monomers; nitrogen-containing monomers such as acrylamide; 2 to 2 such as divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate Monomer having three double bonds; reaction of glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, N-methylol acrylamide, diacetone acrylamide, acetoacetoxyethyl (meth) acrylate, etc. Sex monomer Or it may be you.
(B) The monomer having an ethylenic double bond preferably contains the above-mentioned (b4) unsaturated carboxylic acid, and (b4) the unsaturated carboxylic acid can improve the polymerizability.
尚、（Ｂ）エチレン性二重結合を有する単量体は、アルキル基の炭素数が１８以上であるアクリル（メタ）アクリル酸エステルを含まない。更に、アルキル基の炭素数が１６を超えるアルキル（メタ）アクリル酸エステルを含まないことが、（Ｂ）エチレン性二重結合を有する単量体の重合性、得られるアクリル系樹脂組成物の基材密着性の点から特に好ましい。 In addition, the monomer which has (B) ethylenic double bond does not contain the acrylic (meth) acrylic acid ester whose carbon number of an alkyl group is 18 or more. Furthermore, the fact that the alkyl group does not contain an alkyl (meth) acrylic acid ester having more than 16 carbon atoms, (B) the polymerizability of the monomer having an ethylenic double bond, the group of the resulting acrylic resin composition This is particularly preferable from the viewpoint of material adhesion.
更に、（Ｂ）エチレン性二重結合を有する単量体は、アルキル（メタ）アクリレート以外の単量体であって、エチレン性二重結合を有し炭素数が１８以上のアルキル基を有する単量体を含まない。更にまた、（Ｂ）エチレン性二重結合を有する単量体は、アルキル（メタ）アクリレート以外の単量体であって、エチレン性二重結合を有し炭素数が１６を超えるアルキル基を有する単量体を含まないことが、（Ｂ）エチレン性二重結合を有する単量体の重合性、得られるアクリル系樹脂組成物の基材密着性の点から特に好ましい。 Further, (B) the monomer having an ethylenic double bond is a monomer other than an alkyl (meth) acrylate, and a monomer having an ethylenic double bond and an alkyl group having 18 or more carbon atoms. Does not contain a mass. Furthermore, (B) the monomer having an ethylenic double bond is a monomer other than an alkyl (meth) acrylate, and has an ethylenic double bond and an alkyl group having more than 16 carbon atoms. It is especially preferable not to contain a monomer from the viewpoint of (B) the polymerizability of the monomer having an ethylenic double bond and the substrate adhesion of the resulting acrylic resin composition.
本発明では、（Ａ）と（Ｂ）の総和を１００重量部として、０．５〜２４重量部の（Ａ）と９９．５重量部〜７６重量部の（Ｂ）が共重合されるが、１０〜２０重量部の（Ａ）と９０〜８０重量部の（Ｂ）が共重合されることがより好ましい。（Ａ）が０．５重量部未満である場合防湿性に劣り、（Ａ）が２４重量部を超えた場合、上塗り剤を塗工した場合ハジキを生ずる。 In the present invention, the total of (A) and (B) is 100 parts by weight, and 0.5 to 24 parts by weight of (A) and 99.5 to 76 parts by weight of (B) are copolymerized. More preferably, 10 to 20 parts by weight of (A) and 90 to 80 parts by weight of (B) are copolymerized. When (A) is less than 0.5 parts by weight, the moisture resistance is inferior. When (A) exceeds 24 parts by weight, repelling occurs when a top coat is applied.
（Ｂ）が（ｂ３）を含む場合、（ｂ３）の含有量は（Ａ）アルキル（メタ）アクリル酸エステルと（Ｂ）エチレン性二重結合を有する単量体との総和を１００重量部として、０．０１〜５重量部であることが好ましく、０．１〜３重量部であることが好ましい。（ｂ３）の含有量が０．０１〜５重量部の場合、基材密着性が向上し得、０．１〜３重量部の場合、防水性を損なわず、基材密着性を向上し得るので、更に好ましい。（ｂ３）の含有量が５重量部を超える場合、重合性の低下及び造膜性の低下を生じ得、その結果、防水性及び防湿性も低下し得る。 When (B) contains (b3), the content of (b3) is 100 parts by weight of the sum of (A) alkyl (meth) acrylate and (B) monomer having an ethylenic double bond. 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight. When the content of (b3) is 0.01 to 5 parts by weight, the base material adhesion can be improved, and when it is 0.1 to 3 parts by weight, the base material adhesiveness can be improved without impairing waterproofness. Therefore, it is more preferable. When the content of (b3) exceeds 5 parts by weight, the polymerizability and the film forming property may be lowered, and as a result, the waterproof property and the moisture proof property may also be lowered.
（Ｂ）が（ｂ４）を含む場合、（ｂ４）の含有量は（Ａ）アルキル（メタ）アクリル酸エステルと（Ｂ）エチレン性二重結合を有する単量体との総和を１００重量部として、０．５〜５重量部であることが好ましく、１〜３重量部であることが好ましい。（ｂ４）の含有量が０．５〜５重量部である場合、重合性について好ましく、（ｂ４）の含有量が１〜３重量部である場合、重合性についてより好ましい。 When (B) contains (b4), the content of (b4) is 100 parts by weight of the sum of (A) alkyl (meth) acrylate and (B) monomer having an ethylenic double bond. 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight. When content of (b4) is 0.5-5 weight part, it is preferable about polymerizability, and when content of (b4) is 1-3 weight part, it is more preferable about polymerizability.
本発明のアクリル系樹脂は上述の単量体（Ａ）及び（Ｂ）を、公知のラジカル重合方法を用いて重合することで得ることができる。そのような重合方法として例えば、塊状重合、溶液重合、懸濁重合、乳化重合を例示できる。
これらの重合のうち、乳化重合が特に好ましい。乳化重合は水を媒体とした乳化剤を用いたラジカル重合であり、公知の方法を用いることができる。乳化重合の方法として、例えば、エチレン性二重結合を有する単量体と乳化剤を水性媒体中に仕込んで重合させる方法、エチレン性二重結合を有する単量体と乳化剤を連続的又は間欠的に水性媒体中に滴下して重合させる方法、エチレン性二重結合を有する単量体と乳化剤に水を加えて乳化液を調製し、これを連続的又は間欠的に水性媒体中に滴下して重合させる方法等を例示することができる。
The acrylic resin of the present invention can be obtained by polymerizing the above monomers (A) and (B) using a known radical polymerization method. Examples of such polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
Of these polymerizations, emulsion polymerization is particularly preferred. Emulsion polymerization is radical polymerization using an emulsifier using water as a medium, and a known method can be used. As a method of emulsion polymerization, for example, a method in which a monomer having an ethylenic double bond and an emulsifier are charged in an aqueous medium for polymerization, and a monomer having an ethylenic double bond and an emulsifier are continuously or intermittently used. A method of polymerizing by dropping into an aqueous medium, preparing an emulsion by adding water to a monomer having an ethylenic double bond and an emulsifier, and dropping this into an aqueous medium continuously or intermittently to polymerize The method of making it etc. can be illustrated.
乳化剤はモノマー乳化力を有し、乳化重合の過程ではミセルを形成してモノマーに重合の場を提供し、重合中又は重合後はポリマー粒子の表面に固定化して粒子の分散安定性を図る。乳化剤としては、例えば、アニオン系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤、高分子界面活性剤等を例示できる。 The emulsifier has a monomer emulsifying power. In the process of emulsion polymerization, micelles are formed to provide a field for polymerization to the monomer, and during or after the polymerization, it is immobilized on the surface of the polymer particles to improve the dispersion stability of the particles. Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant.
また、耐水性、耐アルカリ性、及び防水性の向上のために乳化剤の一分子内にラジカル重合可能な二重結合を有する「反応性界面活性剤」を使用するのが好ましい。尚、「反応性界面活性剤」は、（Ｂ）エチレン性二重結合を有する単量体に含まれるものではない。 Moreover, it is preferable to use a “reactive surfactant” having a double bond capable of radical polymerization in one molecule of the emulsifier in order to improve water resistance, alkali resistance and waterproofness. The “reactive surfactant” is not included in the monomer (B) having an ethylenic double bond.
アニオン系界面活性剤として、例えば、
ナトリウムドデシルサルフェート、カリウムドデシルサルフェート等のアルカリ金属アルキルサルフェート；
ナトリウムドデシルポリグリコールエーテルサルフェート；
アンモニウムドデシルサルフェート等のアンモニウムアルキルサルフェート；
ナトリウムスルホシノエート；
スルホン化パラフィンのアルカリ金属塩、スルホン化パラフィンのアンモニウム塩等のアルキルスルホネート；
ナトリウムラウレート、トリエタールアミンオレエート、トリエタールアミンアビエテート等の脂肪酸塩；
ナトリウムドデシルベンゼンスルホネート、アルカリフェノールヒドロキシエチレンのアルカリ金属サルフェート等のアルキルアリールスルホネート；
高アルキルナフタレンスルホン酸塩；
ナフタレンスルホン酸ホルマリン縮合物；
ジアルキルスルホコハク酸塩；
ポリオキシエチレンアルキルサルフェート塩；
ポリオキシエチレンアルキルアリールサルフェート塩
等を例示できる。
As an anionic surfactant, for example,
Alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate;
Sodium dodecyl polyglycol ether sulfate;
Ammonium alkyl sulfates such as ammonium dodecyl sulfate;
Sodium sulfosinoate;
Alkyl sulfonates such as alkali metal salts of sulfonated paraffin and ammonium salts of sulfonated paraffin;
Fatty acid salts such as sodium laurate, trietalamine oleate, trietalamine abiate;
Alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate, alkali metal sulfate of alkali phenol hydroxyethylene;
High alkyl naphthalene sulfonate;
Naphthalenesulfonic acid formalin condensate;
Dialkyl sulfosuccinates;
Polyoxyethylene alkyl sulfate salts;
Examples thereof include polyoxyethylene alkylaryl sulfate salts.
ノニオン系界面活性剤として、例えば、
ポリオキシエチレンアルキルエーテル；
ポリオキシエチレンアルキルアリールエーテル；
ソルビタン脂肪酸エステル；
ポリオキシエチレンソルビタン脂肪酸エステル；
グリセロールのモノラウレート等の脂肪酸モノグリセライド；
ポリオキシエチレンオキシプロピレン共重合体；
エチレンオキサイドと脂肪族アミン、アミド又は酸との縮合生成物
等を例示できる。
As a nonionic surfactant, for example,
Polyoxyethylene alkyl ethers;
Polyoxyethylene alkyl aryl ethers;
Sorbitan fatty acid ester;
Polyoxyethylene sorbitan fatty acid ester;
Fatty acid monoglycerides such as monolaurate of glycerol;
Polyoxyethyleneoxypropylene copolymer;
Examples include condensation products of ethylene oxide and aliphatic amines, amides or acids.
カチオン系界面活性剤として、例えば、
モノアルキルアンモニウム塩、ジアルキルアンモニウム塩、エチレンオキサイド付加型アルキルアンモニウム塩等を例示できる。
As a cationic surfactant, for example,
Examples thereof include monoalkyl ammonium salts, dialkyl ammonium salts, ethylene oxide addition type alkyl ammonium salts, and the like.
両性界面活性剤として、例えば、
アミドプロピルベタイン、アミノ酢酸ベタイン等を例示できる。
As an amphoteric surfactant, for example,
Examples include amidopropyl betaine and aminoacetic acid betaine.
高分子界面活性剤として、例えば、
ポリビニルアルコール；
ポリ（メタ）アクリル酸ナトリウム、ポリ（メタ）アクリル酸カリウム、ポリ（メタ）アクリル酸アンモニウム；
ポリ（メタ）アクリレート等を例示できる。
As a polymeric surfactant, for example,
Polyvinyl alcohol;
Sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate;
Examples thereof include poly (meth) acrylate.
反応性界面活性剤として、例えば、ポリオキシエチレンアリルグリシジルノニルフェニルエーテルの硫酸エステル塩（アデカリアソープＳＥシリーズ、旭電化工業社製）、α−スルホ−ω−（１−（アルコキシ）メチル−２−（２−プロペニルオキシ）エトキシ）−ポリ（オキシ−１，２−エタンジイル）のアンモニウム塩（アデカリアソープＳＲシリーズ、旭電化工業社製）、ポリオキシエチレン（又はアルキレン）アルキル（又はアルケニル）エーテル硫酸アンモニウム塩（ＰＤシリーズ、花王社製）、スルホコハク酸型反応性活性剤（ラテムル１８０シリーズ、花王社製）、アルキルアリルスルホコハク酸ナトリウム塩（エレミノールＪＳ−２、三洋化成工業社製）、ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸エステルアンモニウム塩（アクアロンＨＳシリーズ、第一工業製薬社製）、ポリオキシエチレン−１−（アリルオキシメチル）アルキルエーテル硫酸エステルアンモニウム塩（アクアロンＫＨシリーズ、第一工業製薬社製）、ポリオキシエチレンアリルグリシジルノニルフェニルエーテル（アデカリアソープＮＥシリーズ、旭電化工業社製）、ポリオキシエチレンノニルプロペニルエーテル（アクアロンＲＮシリーズ、第一工業製薬社製）、α−ヒドロ−ω−（１−（アルコキシ）メチル−２−（プロペニルオキシ）エトキシ）−ポリ（オキシ−１，２−エタンジイル）（アデカリアソープＥＲシリーズ、旭電化工業社製）等を例示できる。
これらは単独で又は２種以上併せて用いられる。これらの中でも、アルキルアリルスルホコハク酸ナトリウム塩（エレミノールＪＳ−２、三洋化成工業社製）が好ましい。
Examples of reactive surfactants include polyoxyethylene allyl glycidyl nonyl phenyl ether sulfate (Adekaria soap SE series, manufactured by Asahi Denka Kogyo Co., Ltd.), α-sulfo-ω- (1- (alkoxy) methyl-2) -(2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt (ADEKA rear soap SR series, manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene (or alkylene) alkyl (or alkenyl) ether Ammonium sulfate (PD series, manufactured by Kao Corporation), sulfosuccinic acid type reactive activator (Latemul 180 series, manufactured by Kao Corporation), alkylallylsulfosuccinic acid sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries), polyoxyethylene Nonylpropenyl phenyl ether sulfate Ammonium salt (Aqualon HS series, manufactured by Daiichi Kogyo Seiyaku), polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt (Aqualon KH series, manufactured by Daiichi Kogyo Seiyaku), polyoxyethylene allyl glycidyl Nonylphenyl ether (Adekaria soap NE series, manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene nonylpropenyl ether (Aqualon RN series, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), α-hydro-ω- (1- (alkoxy) methyl- Examples include 2- (propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (Adekaria soap ER series, manufactured by Asahi Denka Kogyo Co., Ltd.).
These may be used alone or in combination of two or more. Among these, alkylallylsulfosuccinic acid sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) is preferable.
本発明では、乳化剤の添加量は、（Ａ）と（Ｂ）の総和を１００重量部として、０．１〜２０重量部であることが好ましく、０．５〜３重量部であることがより好ましい。乳化剤の添加量が０．１重量部未満である場合（Ａ）と（Ｂ）との重合性が困難になり得、乳化剤の添加量が２０重量部を超えると、得られたアクリル系樹脂の耐水性が劣り得る傾向が見られる。 In the present invention, the amount of the emulsifier added is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 3 parts by weight, with the total of (A) and (B) being 100 parts by weight. preferable. When the addition amount of the emulsifier is less than 0.1 parts by weight, the polymerizability between (A) and (B) may be difficult, and when the addition amount of the emulsifier exceeds 20 parts by weight, the acrylic resin obtained There is a tendency for water resistance to be inferior.
重合に際しては、（Ａ）と（Ｂ）とを重合させるために重合開始剤が使用される。重合開始剤として、水溶性又は油溶性の過硫酸塩、過酸化物、アゾビス化合物等を例示できる。例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、ジイソプロピルベンゼンハイドロパーオキサイド、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、ｔ−ブチルパーオキシベンゾエート、２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２−ジアミノプロパン）ハイドロクロライド、２，２−アゾビス（２，４−ジメチルバレロニトリル）等を更に例示できる。また、重亜硫酸ナトリウム、ロンガリット、Ｌ−アスコルビン酸、塩化第一鉄、有機アミン等の還元剤を併用したレドックス開始剤を使用することもできる。本発明では、過硫酸ナトリウムが好ましい。 In the polymerization, a polymerization initiator is used to polymerize (A) and (B). Examples of the polymerization initiator include water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like. For example, potassium persulfate, sodium persulfate, ammonium persulfate, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2 , 2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like. Moreover, the redox initiator which used together reducing agents, such as sodium bisulfite, Rongalite, L-ascorbic acid, ferrous chloride, an organic amine, can also be used. In the present invention, sodium persulfate is preferred.
上記重合開始剤の使用量は、（Ａ）と（Ｂ）の総和１００重量部に対して、０．０５〜５重量部であることが好ましく、０．１〜２重量部であることがより好ましい。 The amount of the polymerization initiator used is preferably 0.05 to 5 parts by weight and more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the sum of (A) and (B). preferable.
また、乳化重合に際しては、樹脂の分子量を調整するために必要に応じて連鎖移動剤を使用することができる。
上記連鎖移動剤として、例えば、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ブチルメルカプタン、２−エチルヘキシルチオグリコレート、２−メルカプトエタノール、トリクロロブロモメタン等を例示することができる。
上記連鎖移動剤の使用量は、（Ａ）と（Ｂ）の総和を１００重量部として、０〜５重量部程度であることが好ましい。
In emulsion polymerization, a chain transfer agent can be used as necessary to adjust the molecular weight of the resin.
Examples of the chain transfer agent include n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, trichlorobromomethane and the like.
The amount of the chain transfer agent used is preferably about 0 to 5 parts by weight, with the total of (A) and (B) being 100 parts by weight.
乳化重合により得られたアクリル系樹脂は安定性を保つために、必要であれば、アンモニア、各種有機アミン類、水酸化ナトリウム等でアルカリ性領域のｐＨ、即ち、７．５〜９．０に調整することが望ましい。 In order to maintain the stability of the acrylic resin obtained by emulsion polymerization, the pH in the alkaline region, that is, 7.5 to 9.0 is adjusted with ammonia, various organic amines, sodium hydroxide or the like, if necessary. It is desirable to do.
本発明に係るアクリル系樹脂は、防湿性を有する防湿アクリル系樹脂として好適に使用することができる。本発明において「防湿」とは、後述する実施例に記載の防水性及び防湿性の評価方法を用いて、防水性及び防湿性を評価して、防水性については、透水量が、０．２ｍｌ以下又は防湿性については、透湿量が７５ｇ／ｍ２以下であることをいう。
好ましくは、防水性については、透水量が、０．２ｍｌ以下及び防湿性については、透湿量が７５ｇ／ｍ２以下である。より好ましくは、防水性については、透水量が、０．１ｍｌ以下及び防湿性については、透湿量が７５ｇ／ｍ２以下であり、またより好ましくは、防水性については、透水量が、０．２ｍｌ以下及び防湿性については、透湿量が５５ｇ／ｍ２以下である。特に好ましくは、防水性については、透水量が、０．１ｍｌ以下及び防湿性については、透湿量が５５ｇ／ｍ２以下であることをいう。
The acrylic resin according to the present invention can be suitably used as a moisture-proof acrylic resin having moisture resistance. In the present invention, the term “moisture-proof” refers to waterproof and moisture-proof evaluation methods using the waterproof and moisture-proof evaluation methods described in the examples described later, and the water permeability is 0.2 ml. Hereinafter, or about moisture resistance, it means that the moisture permeability is 75 g / m 2 or less.
Preferably, the water permeability is 0.2 ml or less for waterproofing, and the moisture permeability is 75 g / m 2 or less for moisture resistance. More preferably, for water resistance, the water permeability is 0.1 ml or less, and for moisture resistance, the moisture permeability is 75 g / m 2 or less, and more preferably, for water resistance, the water permeability is 0. About 2 ml or less and moisture resistance, the moisture permeability is 55 g / m 2 or less. Particularly preferably, the water permeability is 0.1 ml or less for waterproofness and the moisture permeability is 55 g / m 2 or less for moisture resistance.
本発明は、上記アクリル系樹脂を含有するアクリル系樹脂組成物を提供する。
上記アクリル系樹脂組成物は、当業者に周知の顔料、防錆剤、増粘剤、分散剤、消泡剤、防腐剤、成膜助剤等を必要に応じて含有してよい。
The present invention provides an acrylic resin composition containing the above acrylic resin.
The acrylic resin composition may contain pigments, rust preventives, thickeners, dispersants, antifoaming agents, preservatives, film forming aids, and the like that are well known to those skilled in the art.
顔料とは、通常、顔料とされるものであれば特に限定されることはない。顔料は、通常、有機顔料と無機顔料に分類される。
有機顔料として、例えば、ファストエロ、ジアゾエロー、ジアゾオレンジ及びナフトールレッド等の不溶性アゾ顔料、銅フタロシアニン等のフタロシアニン系顔料、ファナールレーキ、タンニンレーキ及びカタノール等の染色レーキ、イソインドリノエローグリーニッシュ及びイソエンドリノエローレディッシュ等のイソインドリノ系顔料、キナクリドン系顔料、ペリレンスーカット及びペリレンマルーン等のペリレン系顔料等を例示できる。
無機顔料として、例えば、カーボンブラック、鉛白、鉛丹、黄鉛、銀朱、群青、酸化コバルト、二酸化チタン、チタニウムイエロー、ストロンチウムクロメート、モリブテン赤、モリブテンホワイト、鉄黒、リトボン、エメラルドグリーン、ギネー緑、コバルト青等を例示できる。
The pigment is not particularly limited as long as it is usually a pigment. Pigments are usually classified into organic pigments and inorganic pigments.
Examples of organic pigments include, for example, insoluble azo pigments such as fast erotic, diazo yellow, diazo orange and naphthol red, phthalocyanine pigments such as copper phthalocyanine, dye lakes such as fanal lake, tannin lake and katanol, isoindolino ero greenish and Illustrative examples include isoindolino pigments such as Isoendolino Yellow Dish, perylene pigments such as quinacridone pigments, perylene cut and perylene maroon.
Examples of inorganic pigments include carbon black, lead white, red lead, yellow lead, silver vermilion, ultramarine, cobalt oxide, titanium dioxide, titanium yellow, strontium chromate, molybden red, molybten white, iron black, litbon, emerald green, guinea green. And cobalt blue.
充填剤とは、性能向上、コスト低減等の目的で添加される物質をいい、通常充填剤とされるものであれば、特に制限されるものではない。具体的には、炭酸カルシウム、炭酸マグネシウム、シリカ、タルク、クレー、アルミナ等を例示できる。
防錆剤とは、素材の腐食を抑制するために加えられる物質をいい、通常、防錆剤とされるものであれば、特に制限されるものではない。例えば、鉛丹、白鉛、亜鉛化鉛、塩基性硫酸白鉛、塩基性クロム酸鉛、鉛酸カルシウム、クロム酸亜鉛、鉛酸シアナミド、亜粉末、ジクロロメート、バリウムクロメート、亜硝酸ソーダ、ジシクロヘキシルアンモニウムニトリル、シクロヘキシルアミンカーボネート、防錆油等を例示できる。
さらに、上述のアクリル系樹脂組成物には必要に応じて種々性能を上げる目的で他の樹脂を混和することもできる。他の樹脂として例えば、キシレン樹脂、アルキド樹脂、ウレタン樹脂、エポキシ樹脂、アクリル樹脂、タッキファイヤー、ワックスエマルジョン等を例示できる。
The filler refers to a substance added for the purpose of improving performance, reducing costs, and the like, and is not particularly limited as long as it is normally used as a filler. Specific examples include calcium carbonate, magnesium carbonate, silica, talc, clay, and alumina.
A rust preventive agent refers to a substance added to suppress corrosion of a material, and is not particularly limited as long as it is generally regarded as a rust preventive agent. For example, red lead, white lead, zinc lead, basic white lead sulfate, basic lead chromate, calcium lead acid, zinc chromate, lead acid cyanamide, powder, dichloromate, barium chromate, sodium nitrite, dicyclohexyl Examples thereof include ammonium nitrile, cyclohexylamine carbonate, rust preventive oil and the like.
Furthermore, other resins can be mixed with the above-mentioned acrylic resin composition as necessary for the purpose of improving various performances. Examples of other resins include xylene resin, alkyd resin, urethane resin, epoxy resin, acrylic resin, tackifier, and wax emulsion.
本明細書において、混和とは、「混合」及び「分散」の双方を含むこととする。「混合」及び「分散」する方法として、通常使用されている方法、例えばボールミキサー、ホモジナイザー又は羽付き攪拌機等の混合機を用いる方法を使用することができる。「混合」及び「分散」することができる限り、これら混合機の使用について特に制限されることはない。 In this specification, “mixing” includes both “mixing” and “dispersing”. As a method of “mixing” and “dispersing”, a commonly used method, for example, a method using a mixer such as a ball mixer, a homogenizer, or a bladed stirrer can be used. As long as “mixing” and “dispersing” can be performed, the use of these mixers is not particularly limited.
上記方法で得られた本発明に係る「アクリル系樹脂組成物」は、無機質成形部材に好適に使用することができ、特に、例えば、ＡＬＣ板、セメント板及び瓦等の無機質成形板に塗工（又は塗布）して使用される。ここで「塗工」とは、アクリル系樹脂組成物を塗工する方法として通常用いられる方法であれば、限定されることなく使用できる。例えば、ロールコーター、カーテンフローコーターおよびスプレー塗装等の塗料を塗工する方法及び塗料を塗布する方法を例示できる。 The “acrylic resin composition” according to the present invention obtained by the above method can be suitably used for inorganic molded members, and in particular, coated on inorganic molded plates such as ALC plates, cement plates and roof tiles. (Or applied) and used. Here, “coating” can be used without limitation as long as it is a method usually used as a method of coating an acrylic resin composition. For example, a method of applying a paint such as a roll coater, a curtain flow coater, and spray coating, and a method of applying the paint can be exemplified.
尚、上述のアクリル系樹脂組成物は、上塗り剤としても下塗り剤（中塗り剤及びいわゆるシーラーを含む）としても使用できるが、下塗り剤、特にシーラーとして使用することが好ましい。ここで「上塗り剤」とは、トップコートとも呼ばれ、最も外側に塗工される塗料をいい、外観の向上、つやだし、耐水性の向上、耐候性の向上等を目的として塗工される塗料をいう。一方、「下塗り剤」とは、上塗り剤以外の塗料をいい、主に防水性、防湿性、基材密着性の向上等を目的として、基材に直接塗工されるシーラー（下地調整剤又はプライマーと呼ばれることもある）、並びに主に上塗り剤とシーラーとの間をつなぎ、防水性、防湿性、耐ブリスター性の向上等を目的として塗工される中塗り剤を含む。 In addition, although the above-mentioned acrylic resin composition can be used as both a topcoat and an undercoat (including an intermediate coat and a so-called sealer), it is preferably used as an undercoat, particularly a sealer. Here, the “top coat” is also referred to as a top coat, which is a paint applied on the outermost side, and is applied for the purpose of improving the appearance, polishing, improving water resistance, improving weather resistance, etc. It refers to paint. On the other hand, “undercoat” refers to paints other than the topcoat, and is mainly used for the purpose of improving waterproofness, moisture proofing, adhesion to the substrate, etc. In some cases, it is also referred to as a primer), and an intermediate coating agent is applied mainly for the purpose of improving waterproofness, moisture resistance, blister resistance, etc., connecting between the topcoat and the sealer.
本発明に係るアクリル系樹脂組成物は、防湿性を有する防湿アクリル系樹脂組成物として好適に使用することができる。本発明に係る防湿アクリル系樹脂組成物において「防湿」とは、防湿アクリル系樹脂について記載したことと同様であり、その好ましい範囲、より好ましい範囲及び特に好ましい範囲についても、防湿アクリル系樹脂について記載したことと同様である。 The acrylic resin composition according to the present invention can be suitably used as a moisture-proof acrylic resin composition having moisture resistance. In the moisture-proof acrylic resin composition according to the present invention, “moisture-proof” is the same as described for the moisture-proof acrylic resin, and the preferred range, more preferred range, and particularly preferred range are also described for the moisture-proof acrylic resin. It is the same as that.
本発明に係るアクリル系樹脂組成物は、無機質成形部材用シーラーとして好適である。無機質成形部材とは、例えば、珪酸カルシウム、石膏、ロックウール、コンクリート、セメント、モルタル及びスレート等の無機質の材料が、種々の形態（板、ブロック等）に、例えば、押し出し成形等によって成形された部材をいう。
無機質成形部材の好ましい態様の一つとして、「無機質成形板」を例示できる。「無機質成形板」とは、例えば、珪カル板、セメント系押出し成形板、ＡＬＣ板（軽量気泡コンクリート板）、硬質木片セメント板、瓦及び炭酸マグネシウム板等の無機質の材料が成形された板状の部材をいう。
The acrylic resin composition according to the present invention is suitable as a sealer for inorganic molded members. For example, inorganic materials such as calcium silicate, gypsum, rock wool, concrete, cement, mortar, and slate were formed into various forms (plates, blocks, etc.) by, for example, extrusion molding. Refers to a member.
As one preferred embodiment of the inorganic molded member, an “inorganic molded plate” can be exemplified. “Inorganic molded plate” means, for example, a plate formed of an inorganic material such as a quartz plate, a cement-based extruded plate, an ALC plate (lightweight cellular concrete plate), a hard wood cement plate, a tile, and a magnesium carbonate plate. It means the member.
次に、実施例について比較例と併せて説明する。
まず、アクリル系樹脂を調製するために下記成分を準備した。
（Ａ）成分：アルキル（メタ）アクリル酸エステル
（ａ１−１）ラウリルアクリレート（日本油脂社製）
（ａ２−１）セチルメタクリレート（日本油脂社製）
（Ｂ）成分：エチレン性二重結合を有する単量体
（ｂ１−１）スチレン（和光純薬工業社製）
（ｂ２−１）メチルメタクリレート（和光純薬工業社製）
（ｂ２−２）２−エチルヘキシルアクリレート（和光純薬工業社製）
（ｂ３−１）γ-メタクリロキシプロピルトリメトキシシラン（日本ユニカ社製）
（ｂ４−１）メタクリル酸（和光純薬工業社製）
アルキル基の炭素数が１８であるアルキル（メタ）アクリル酸エステルとして、
（ａ’−１）ステアリルアクリレート（日本油脂社製）
更に、下記添加剤も準備した。
乳化剤（反応性界面活性剤）
アルキルアリルスルホコハク酸ナトリウム塩
（エレミノールＪＳ−２、三洋化成工業社製）
防腐剤
複合型イソチアゾリン系防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ、ソージャパン社製）
消泡剤
疎水性シリカ系消泡剤（ノプコ８０３４、サンノプコ社製）
Next, examples will be described together with comparative examples.
First, the following components were prepared in order to prepare an acrylic resin.
(A) component: alkyl (meth) acrylic acid ester (a1-1) lauryl acrylate (manufactured by NOF Corporation)
(A2-1) Cetyl methacrylate (manufactured by NOF Corporation)
(B) Component: Monomer having an ethylenic double bond (b1-1) Styrene (Wako Pure Chemical Industries, Ltd.)
(B2-1) Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
(B2-2) 2-ethylhexyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
(B3-1) γ-methacryloxypropyltrimethoxysilane (Nippon Unica)
(B4-1) Methacrylic acid (Wako Pure Chemical Industries, Ltd.)
As an alkyl (meth) acrylic acid ester having 18 carbon atoms in the alkyl group,
(A′-1) stearyl acrylate (manufactured by NOF Corporation)
In addition, the following additives were also prepared.
Emulsifier (Reactive surfactant)
Alkylallylsulfosuccinic acid sodium salt
(Eleminol JS-2, manufactured by Sanyo Chemical Industries)
Preservative Composite isothiazoline preservative (ACTICIDE MBS, manufactured by So Japan)
Antifoaming agent Hydrophobic silica-based antifoaming agent (Nopco 8034, manufactured by San Nopco)
実施例１
１重量部の乳化剤（エレミノールＪＳ−２、三洋化成工業社製）を、３０重量部の蒸留水に溶解し、これに（Ａ）成分として、５重量部の（ａ１−１）ラウリルアクリレート、及び（Ｂ）成分として、３０重量部の（ｂ１−１）スチレン、２７重量部の（ｂ２−１）メチルメタクリレート、３６重量部の（ｂ２−２）２−エチルヘキシルアクリレート及び２重量部の（ｂ４−１）メタクリル酸を加えて乳化して、乳化液（又はエマルジョン）を調製した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、６０重量部の蒸留水及び１重量部の乳化剤（エレミノールＪＳ−２、三洋化成工業社製）を加え、窒素ガスを吹き込みながら攪拌しながら加熱して、液温を７５℃に調節した。これに、まず、先に調製した乳化液の約５体積％の部分と、開始剤水溶液（０．２重量部の過硫酸ナトリウムを１０重量部の蒸留水に溶解したもの）の１０体積％の部分を、攪拌しながら加えた後、さらに乳化液の残りの部分と開始剤水溶液の残りの部分の各々を約３時間かけて、攪拌しながら、滴下して反応させた。更に、同温度（７５℃）で、約１時間攪拌を続けて反応を完結させた。得られた反応混合物を冷却後、アンモニア水を加えてｐＨを９に調整して、実施例１のアクリル系樹脂を得た。更に、０．２重量部の防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ、ソージャパン社製）、０．１重量部の消泡剤（ノプコ８０３４、サンノプコ社製）を加えて、実施例１のアクリル系樹脂組成物を得た。
Example 1
1 part by weight of emulsifier (Eleminol JS-2, manufactured by Sanyo Kasei Kogyo Co., Ltd.) is dissolved in 30 parts by weight of distilled water, and (A) component 5 parts by weight of (a1-1) lauryl acrylate, and As component (B), 30 parts by weight of (b1-1) styrene, 27 parts by weight of (b2-1) methyl methacrylate, 36 parts by weight of (b2-2) 2-ethylhexyl acrylate, and 2 parts by weight of (b4- 1) Emulsion (or emulsion) was prepared by adding methacrylic acid and emulsifying. On the other hand, to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, 60 parts by weight of distilled water and 1 part by weight of an emulsifier (Eleminol JS-2, manufactured by Sanyo Chemical Industries) are added. The liquid temperature was adjusted to 75 ° C. by heating with stirring while blowing nitrogen gas. First, about 5% by volume of the previously prepared emulsion and 10% by volume of an aqueous initiator solution (0.2 parts by weight of sodium persulfate dissolved in 10 parts by weight of distilled water). After the portion was added with stirring, each of the remaining portion of the emulsion and the remaining portion of the initiator aqueous solution was dropped and reacted for about 3 hours with stirring. Further, stirring was continued for about 1 hour at the same temperature (75 ° C.) to complete the reaction. After cooling the obtained reaction mixture, aqueous ammonia was added to adjust the pH to 9, and the acrylic resin of Example 1 was obtained. Further, 0.2 parts by weight of an antiseptic (ACTICIDE MBS, manufactured by So Japan Co., Ltd.) and 0.1 parts by weight of an antifoaming agent (Nopco 8034, manufactured by San Nopco) were added, and the acrylic resin composition of Example 1 was added. Got.
実施例２〜８
表１に示すような種類の成分を、表１に示すような量で用い、実施例１と同様の方法を用いて実施例２〜８のアクリル系樹脂を得た。尚、実施例７、８では（Ａ）成分の一種として、（ａ２−１）セチルメタクリレートを配合した。実施例１と同様に、０．２重量部の防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ、ソージャパン社製）及び０．１重量部の消泡剤（ノプコ８０３４、サンノプコ社製）を各アクリル系樹脂組成物に添加して、実施例２〜８のアクリル系樹脂組成物を得た。
Examples 2-8
Using the same kind of components as shown in Table 1 in the amounts shown in Table 1, acrylic resins of Examples 2 to 8 were obtained using the same method as in Example 1. In Examples 7 and 8, (a2-1) cetyl methacrylate was blended as a kind of component (A). In the same manner as in Example 1, 0.2 parts by weight of an antiseptic (ACTICIDE MBS, manufactured by So Japan Co., Ltd.) and 0.1 parts by weight of an antifoaming agent (Nopco 8034, manufactured by San Nopco) were added to each acrylic resin composition. It added and the acrylic resin composition of Examples 2-8 was obtained.
実施例９〜１１
（ｂ３）エチレン性二重結合を有するアルコキシシランとして、（ｂ３−１）γ-メタクリロキシプロピルトリメトキシシラン（日本ユニカー社製）を、（ｂ１−１）スチレン、（ｂ２−１）メチルメタクリレート、（ｂ２−２）２−エチルヘキシルアクリレート、（ｂ４−１）メタクリル酸と共に用いた。表１に示すような割合で各成分を用い、実施例１と同様に重合して、実施例９〜１１のアクリル系樹脂を得た。更に０．２重量部の防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ、ソージャパン社製）、０．１重量部の消泡剤（ノプコ８０３４、サンノプコ社製）を添加して、実施例９〜１１のアクリル系樹脂組成物を得た。
Examples 9-11
(B3) As an alkoxysilane having an ethylenic double bond, (b3-1) γ-methacryloxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd.), (b1-1) styrene, (b2-1) methyl methacrylate, (B2-2) 2-ethylhexyl acrylate, (b4-1) Used together with methacrylic acid. Polymerization was carried out in the same manner as in Example 1 using the respective components in proportions as shown in Table 1, and acrylic resins of Examples 9 to 11 were obtained. Further, 0.2 parts by weight of an antiseptic (ACTICIDE MBS, manufactured by So Japan Co., Ltd.) and 0.1 parts by weight of an antifoaming agent (Nopco 8034, manufactured by San Nopco) were added, and the acrylic resins of Examples 9-11 A composition was obtained.
比較例１〜５
表１に示すような割合で各成分を用いて、実施例１と同様に重合して、比較例１〜５のアクリル系樹脂を得た。実施例１と同様に０．２重量部の防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ、ソージャパン社製）、０．１重量部の消泡剤（ノプコ８０３４、サンノプコ社製）を添加して、比較例１〜５のアクリル系樹脂組成物を得た。
Comparative Examples 1-5
Polymerization was carried out in the same manner as in Example 1 using the respective components in proportions as shown in Table 1, and acrylic resins of Comparative Examples 1 to 5 were obtained. In the same manner as in Example 1, 0.2 parts by weight of an antiseptic (ACTICIDE MBS, manufactured by So Japan Co., Ltd.) and 0.1 parts by weight of an antifoaming agent (Nopco 8034, manufactured by San Nopco) were added. 5 acrylic resin composition was obtained.
アクリル系樹脂組成物の評価方法
実施例及び比較例のアクリル系樹脂組成物の評価は以下の様に行った。
［防水性］
ＪＩＳ Ａ６９０９（透水試験Ｂ法）に準拠して、透水量を測定することによって行った。即ち、各樹脂組成物を１５重量％の水溶液となるように希釈し、また、必要であれば適宜ブチルセロソルブ（可塑剤）を加えて最低造膜温度を０℃に低下させ試験液とした。この試験液をケイカル板（比重０．８）に１００ｇ／ｍ２の量となるようにはけ塗りし、１００℃にて１０分間乾燥して塗板を作製した。４４ｃｍ２の面積の塗板を１日で透過する水量（ｍｌ）を測定することで透水量を測定した。透水量が大きいほど防水性は小さく、透水量が小さいほど防水性が大きい。評価結果は以下のように表示した。
◎：透水量は０．１ｍｌ以下である。
○：透水量は０．１ｍｌより多く、０．２ｍｌ以下である。
×：透水量は０．２ｍｌより多い。
Evaluation Method of Acrylic Resin Composition Evaluation of the acrylic resin compositions of Examples and Comparative Examples was performed as follows.
[Waterproof]
Based on JIS A6909 (water permeability test B method), it measured by measuring the amount of water permeation. That is, each resin composition was diluted to an aqueous solution of 15% by weight, and if necessary, butyl cellosolve (plasticizer) was appropriately added to lower the minimum film-forming temperature to 0 ° C. to prepare a test solution. This test solution was brushed on a calcium plate (specific gravity 0.8) so as to have an amount of 100 g / m 2 and dried at 100 ° C. for 10 minutes to prepare a coated plate. The amount of water permeated was measured by measuring the amount of water (ml) that permeated through a coated plate having an area of 44 cm 2 in one day. The greater the water permeability, the smaller the waterproofness, and the smaller the water permeability, the greater the waterproofness. The evaluation results were displayed as follows.
A: Water permeability is 0.1 ml or less.
○: Water permeability is more than 0.1 ml and 0.2 ml or less.
X: Water permeability is more than 0.2 ml.
［防湿性］
各樹脂組成物を３５重量％の水溶液となるように希釈し、必要であれば適宜ブチルセロソルブ（可塑剤）を加えて最低造膜温度を０℃に低下させ試験液とした。次に、５ｍｉｌ又は１０ｍｉｌのアプリケーターを用いて、この試験液を濾紙（東洋濾紙社製 ♯１３１）に塗工し、１００℃で１０分間乾燥して塗工紙を作製した。塗工紙を直径が３．４ｃｍである円形に切断した後、瞬間接着剤を用いて予め１０ｇの塩化カルシウムを入れたシャーレ（直径３ｃｍ）の上部に隙間が生じないように接着し、濾紙を接着したシャーレの重量を測定した。さらに、硝酸バリウム飽和水溶液を入れたデシケーターの中に上述の濾紙を接着したシャーレを並べた後、デシケーターを２０℃、湿度６５％の恒温室内に保管した。定常状態と成った後、濾紙を接着したシャーレの重量を測定し、試験前の重量との差から透湿量（ｇ／ｍ２）を求めて、防湿性を評価した。透湿量が大きいほど防湿性は小さく、透湿量が小さいほど防湿性は大きい。評価結果は以下のように表示した。
◎：大変良好であり、透湿量は５５ｇ／ｍ２以下である。
○：良好であり、透湿量は５５ｇ／ｍ２より多く、７５ｇ／ｍ２以下である。
×：不良であり、透湿量は７５ｇ／ｍ２より多い。
[Moisture resistance]
Each resin composition was diluted to an aqueous solution of 35% by weight, and if necessary, butyl cellosolve (plasticizer) was appropriately added to lower the minimum film forming temperature to 0 ° C. to prepare a test solution. Next, using a 5 mil or 10 mil applicator, this test solution was applied to filter paper (# 131 manufactured by Toyo Roshi Kaisha, Ltd.) and dried at 100 ° C. for 10 minutes to prepare a coated paper. After the coated paper is cut into a circle with a diameter of 3.4 cm, it is bonded using an instantaneous adhesive so that there is no gap at the top of the petri dish (diameter 3 cm) containing 10 g of calcium chloride in advance. The weight of the adhered petri dish was measured. Furthermore, after arranging the petri dish which adhere | attached the above-mentioned filter paper in the desiccator which put barium nitrate saturated aqueous solution, the desiccator was stored in the constant temperature room of 20 degreeC and 65% of humidity. After the steady state was reached, the weight of the petri dish to which the filter paper was adhered was measured, and the moisture permeability (g / m 2 ) was determined from the difference from the weight before the test to evaluate moisture resistance. The greater the moisture permeability, the smaller the moisture resistance, and the smaller the moisture permeability, the greater the moisture resistance. The evaluation results were displayed as follows.
(Double-circle): It is very favorable and moisture permeability is 55 g / m < 2 > or less.
○: Good, moisture permeability is more than 55 g / m 2 and 75 g / m 2 or less.
X: Poor and moisture permeability is more than 75 g / m 2 .
［上塗りハジキ性］
各樹脂組成物を１５重量％の水溶液となるように希釈し、また、必要であれば適宜ブチルセロソルブ（可塑剤）を加えて最低造膜温度を０℃に低下させ試験液とした。この試験液を、ケイカル板（比重０．８）に１００ｇ／ｍ２の量となるようにはけ塗りし、１００℃にて１０分間乾燥して塗板を作製した。さらに、上塗り用樹脂組成物（日本エヌエスシー（株）製のヨドゾールＡＤ１３７（商品名））を上述の塗膜の上に１００ｇ／ｍ２の量となるようにはけ塗りした。このときに、塗板上で上塗り用樹脂組成物のハジキの有無、均一に塗布されるか否かを目視にて確認した。評価結果は以下のように表示した。
○：良好であり、上塗り用樹脂組成物は塗板上でハジキがなく、均一に塗布される。
×：不良であり、上塗り用樹脂組成物は塗板上でハジキを生じ、均一に塗布されない。
[Top coat repellent properties]
Each resin composition was diluted to an aqueous solution of 15% by weight, and if necessary, butyl cellosolve (plasticizer) was appropriately added to lower the minimum film forming temperature to 0 ° C. to prepare a test solution. This test solution was brushed on a calcium plate (specific gravity 0.8) so as to have an amount of 100 g / m 2 and dried at 100 ° C. for 10 minutes to prepare a coated plate. Furthermore, a resin composition for top coating (Yodosol AD137 (trade name) manufactured by Nippon SC Co., Ltd.) was brushed onto the above-mentioned coating film so as to have an amount of 100 g / m 2 . At this time, the presence or absence of repellency of the resin composition for overcoating on the coated plate and whether it was uniformly applied were confirmed visually. The evaluation results were displayed as follows.
○: Good, and the top coating resin composition is uniformly applied without any repellency on the coated plate.
X: Poor, and the resin composition for top coating causes repelling on the coated plate and is not uniformly applied.
［重合性］
各樹脂重合時の機台汚れ、濾過残渣等から総合判断した。評価結果は以下のように表示した。
◎：大変良好。
○：良好。
×：不良。
[Polymerizability]
Comprehensive judgment was made based on machine stand contamination, filtration residue, etc. during polymerization of each resin. The evaluation results were displayed as follows.
A: Very good.
○: Good.
X: Defect.
［基材密着性］
各樹脂組成物を１５重量％の水溶液となるように希釈し、また、必要であれば適宜ブチルセロソルブ（可塑剤）を加えて最低造膜温度を０℃に低下させ試験液とした。この試験液をケイカル板（比重０．８）に１００ｇ／ｍ２の量となるようにはけ塗りし、１００℃にて１０分間乾燥して塗板を作製した。さらに、上塗り用樹脂組成物（日本エヌエスシー（株）製のヨドゾールＡＤ１３７（商品名））を上述の塗膜の上に１００ｇ／ｍ２の量となるようにはけ塗りした。塗板上の皮膜をカッターにて４ｍｍ間隔で碁盤の目状に切り、２５個の桝目を形成し、その上を粘着テープで圧着した。その後、粘着テープを一気に引き剥がし、剥がれずに塗板上に残存した皮膜の面積を確認することで、基材密着性を評価した。皮膜の残存面積が大きいほど、基材密着性は良く、皮膜の残存面積が小さいほど、基材密着性は悪い。評価結果は以下のように表示した。
◎：大変良好であり、皮膜の残存面積は９０％以上である。
○：良好である、皮膜の残存面積は７０％以上、９０％未満である。
△：普通であり、皮膜の残存面積は５０％以上、７０％未満である。
×：不良であり、皮膜の残存面積は５０％未満である。
[Base material adhesion]
Each resin composition was diluted to an aqueous solution of 15% by weight, and if necessary, butyl cellosolve (plasticizer) was appropriately added to lower the minimum film forming temperature to 0 ° C. to prepare a test solution. This test solution was brushed on a calcium plate (specific gravity 0.8) so as to have an amount of 100 g / m 2 and dried at 100 ° C. for 10 minutes to prepare a coated plate. Furthermore, a resin composition for top coating (Yodosol AD137 (trade name) manufactured by Nippon SC Co., Ltd.) was brushed onto the above-mentioned coating film so as to have an amount of 100 g / m 2 . The coating on the coated plate was cut into a grid pattern at intervals of 4 mm with a cutter to form 25 squares, and the top was pressure-bonded with an adhesive tape. Thereafter, the adhesive tape was peeled off at once, and the substrate adhesion was evaluated by confirming the area of the film remaining on the coated plate without being peeled off. The larger the remaining area of the film, the better the substrate adhesion, and the smaller the remaining area of the film, the worse the substrate adhesion. The evaluation results were displayed as follows.
A: Very good, and the remaining area of the film is 90% or more.
Good: The remaining area of the film is 70% or more and less than 90%.
(Triangle | delta): It is normal and the remaining area of a film | membrane is 50% or more and less than 70%.
X: It is defective and the remaining area of the film is less than 50%.
表１に示すように、実施例の樹脂組成物はいずれも防水性、防湿性、重合性、基材密着性に優れ、上塗りを塗工してもハジキが見られないことがわかる。
これに対し比較例１、比較例２の樹脂は（Ａ）成分である長鎖アルキル基を有するアルキル（メタ）アクリル酸エステルの量が少ないため、防水性、防湿性が劣ると考えられる。また、比較例３の樹脂は（Ａ）成分である長鎖アルキル基を有するアルキル（メタ）アクリル酸エステルの量が多いため上塗りを塗工したときにハジキが発生すると考えられる。比較例４の樹脂は、アルキル基の炭素数が１８であるアルキル（メタ）アクリル酸エステルを含むので、重合性が劣り、更にシーラーとしての基本的な特性である基材密着性も低下し得、良好な基材密着性を得られないことがわかる。
As shown in Table 1, it can be seen that all of the resin compositions of the examples are excellent in waterproofness, moistureproofness, polymerizability, and substrate adhesion, and no repelling is observed even when a top coat is applied.
On the other hand, the resins of Comparative Examples 1 and 2 are considered to be inferior in waterproofness and moisture resistance because the amount of the alkyl (meth) acrylic acid ester having a long chain alkyl group as the component (A) is small. Further, since the resin of Comparative Example 3 has a large amount of the alkyl (meth) acrylate ester having a long-chain alkyl group as the component (A), it is considered that repelling occurs when a top coat is applied. Since the resin of Comparative Example 4 contains an alkyl (meth) acrylic acid ester having an alkyl group with 18 carbon atoms, the polymerizability is inferior, and the base material adhesion, which is a basic property as a sealer, may also be reduced. It can be seen that good substrate adhesion cannot be obtained.
Claims (7)
（Ｂ）エチレン性二重結合を有する単量体：７６〜９９．５重量部とを、
共重合することで得られるアクリル系樹脂であって、
（Ａ）アルキル（メタ）アクリル酸エステルは、
（ａ１）アルキル基の炭素数が１０〜１６であるアルキルアクリル酸エステル及び
（ａ２）アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステル
から選択される少なくとも１種であり、
（Ｂ）エチレン性二重結合を有する単量体は、
（ｂ１）スチレン系誘導体及び
（ｂ２）アルキル基の炭素数が８以下であるアルキル（メタ）アクリル酸エステル
を含むアクリル系樹脂。 (A) alkyl (meth) acrylic acid ester: 0.5 to 24 parts by weight;
(B) Monomer having an ethylenic double bond: 76-99.5 parts by weight
An acrylic resin obtained by copolymerization,
(A) Alkyl (meth) acrylic acid ester is
(A1) at least one selected from alkyl acrylates having 10 to 16 carbon atoms in the alkyl group and (a2) alkyl methacrylates having 14 to 16 carbon atoms in the alkyl group,
(B) The monomer having an ethylenic double bond is
(B1) An acrylic resin containing a styrene derivative and (b2) an alkyl (meth) acrylic acid ester having an alkyl group with 8 or less carbon atoms.
（ａ２）アルキル基の炭素数が１４〜１６であるアルキルメタクリル酸エステルは、セチルメタクリレートである請求項１に記載のアクリル系樹脂。 (A1) The alkyl acrylate ester having 10 to 16 carbon atoms in the alkyl group is lauryl acrylate,
The acrylic resin according to claim 1, wherein the alkyl methacrylate having (a2) an alkyl group having 14 to 16 carbon atoms is cetyl methacrylate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05279617A (en) * | 1992-03-31 | 1993-10-26 | Nippon Synthetic Chem Ind Co Ltd:The | Production of resin for matte coating |
| JPH08239407A (en) * | 1995-03-06 | 1996-09-17 | Kindai Kagaku Kogyo Kk | Moistureproofing agent and its production |
| JP2001163903A (en) * | 1999-12-03 | 2001-06-19 | Toagosei Co Ltd | Method for preparing aqueous emulsion |
| JP2005068442A (en) * | 2004-12-08 | 2005-03-17 | Nisshin Chem Ind Co Ltd | Alkoxysilyl group-containing acrylic emulsion |
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