JP2015166436A - Aqueous anti-rust paint, and alc anti-rust paint film - Google Patents
Aqueous anti-rust paint, and alc anti-rust paint film Download PDFInfo
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- JP2015166436A JP2015166436A JP2014041800A JP2014041800A JP2015166436A JP 2015166436 A JP2015166436 A JP 2015166436A JP 2014041800 A JP2014041800 A JP 2014041800A JP 2014041800 A JP2014041800 A JP 2014041800A JP 2015166436 A JP2015166436 A JP 2015166436A
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- vinylidene chloride
- resin
- mass
- monomer
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- 239000003973 paint Substances 0.000 title claims abstract description 58
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 105
- 239000011248 coating agent Substances 0.000 claims abstract description 68
- 238000000576 coating method Methods 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 67
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 43
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 43
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 230000009477 glass transition Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- -1 acrylic compound Chemical class 0.000 claims description 40
- 230000003449 preventive effect Effects 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 239000004567 concrete Substances 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 55
- 229920006243 acrylic copolymer Polymers 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 18
- 239000000049 pigment Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000002265 prevention Effects 0.000 description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 12
- 229910000077 silane Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 description 11
- 229920001519 homopolymer Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 9
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 229920006026 co-polymeric resin Polymers 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 238000010556 emulsion polymerization method Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
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- 230000007423 decrease Effects 0.000 description 4
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- 239000000377 silicon dioxide Substances 0.000 description 4
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
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- 238000005336 cracking Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
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- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002335 preservative effect Effects 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
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000009 pyrolysis mass spectrometry Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 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
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、水系防錆塗料及びＡＬＣ防錆塗膜に関する。 The present invention relates to a water-based anticorrosive paint and an ALC anticorrosive coating film.
近年、地球環境保護に対する関心が高まるなか、塗料に対する溶剤規制や重金属に対する規制が強化されるなどの影響で溶剤系塗料から水系塗料へ移行する動きが活発となっている。水系塗料へ移行において、溶剤系塗料並みの塗装作業性を維持しつつ、高いレベルの塗膜性能を有する水系塗料が強く望まれている。種々の塗料用樹脂の中で特に塩化ビニリデン系樹脂は、水蒸気透過率や酸素透過率が低いなどのバリア性に優れていることから、防錆塗料用樹脂として好適である。しかしながら塩化ビニリデン系樹脂は耐候性などの機能が乏しく、塩化ビニリデン系樹脂塗膜の上に耐候性に優れる別の塗膜を形成することや、他の樹脂などと混合して使用することなどが必要である。 In recent years, with increasing interest in protecting the global environment, there has been an active movement to shift from solvent-based paints to water-based paints under the influence of stricter restrictions on solvents for paints and heavy metals. In the transition to water-based paints, water-based paints having a high level of coating film performance while maintaining the same painting workability as solvent-based paints are strongly desired. Among various coating resins, vinylidene chloride resins are particularly suitable as rust-preventing coating resins because of their excellent barrier properties such as low water vapor transmission rate and low oxygen transmission rate. However, the vinylidene chloride resin has poor functions such as weather resistance, and it is possible to form another coating film with excellent weather resistance on the vinylidene chloride resin coating film, or to mix it with other resins. is necessary.
このような観点から、耐候性に優れる水系防錆塗料として塩化ビニリデン系共重合エマルションとアクリル系共重合エマルションを混合してなる塗料組成物が特許文献１に開示されている。 From such a viewpoint, Patent Document 1 discloses a coating composition obtained by mixing a vinylidene chloride copolymer emulsion and an acrylic copolymer emulsion as a water-based anticorrosive paint having excellent weather resistance.
しかしながら、特許文献１の塗装組成物は、耐候性や上塗りを重ねて塗装したあとの耐水密着性は発現するものの、例えば、ＡＬＣ（Ａｕｔｏｃｌａｖｅｄ Ｌｉｇｈｔｗｅｉｇｈｔ ａｅｒａｔｅｄ Ｃｏｎｃｒｅｔｅ）木口（軽量気泡コンクリートパネルの切断面）の金属部防錆用途において、冬場の屋外などの低温環境下で塗装作業した際に、乾燥後の塗膜の割れや密着性不足に起因するはく離が発生するなど、低温環境下における防錆塗膜としての本来の機能が発現しにくいという課題がある。 However, although the coating composition of Patent Document 1 exhibits weather resistance and water-resistant adhesion after repeated overcoating, for example, an ALC (Autoclaved Lightweight aerated Concrete) lip (cut surface of lightweight cellular concrete panel) In metal parts rust prevention applications, when coating is performed in low temperature environments such as outdoors in winter, rust prevention coatings in low temperature environments such as cracks after drying and peeling due to insufficient adhesion occur. As a result, there is a problem that the original function is difficult to express.
本発明は、上記課題に鑑みてなされたものであり、耐候性、密着性、及び防錆性に優れる塗膜を形成でき、低温塗装作業性に優れる水系防錆塗料及びＡＬＣ防錆塗膜を提供することを目的とする。 The present invention has been made in view of the above problems, and can form a water-based anticorrosive paint and an ALC anticorrosive paint film that can form a coating film excellent in weather resistance, adhesion, and rust prevention property and that is excellent in low-temperature coating workability. The purpose is to provide.
本発明者らは、上記の問題に鑑み、鋭意研究を重ねた結果、塩化ビニリデン系樹脂と特定のガラス転移温度（Ｔｇ）を有するアクリル系樹脂とを組み合わせることにより、上記課題を解決できることを見いだし、本発明を完成するに至った。 In view of the above problems, the present inventors have conducted extensive research and found that the above problems can be solved by combining a vinylidene chloride resin and an acrylic resin having a specific glass transition temperature (Tg). The present invention has been completed.
即ち、本発明は以下のとおりである。
〔１〕
塩化ビニリデン系樹脂（１）とアクリル系樹脂（２）とを含み、前記アクリル系樹脂（２）のガラス転移温度（Ｔｇ）が−４０℃以上５℃未満であり、前記塩化ビニリデン系樹脂（１）が、塩化ビニリデン単量体単位７０〜９２質量部と、該塩化ビニリデン単量体と共重合可能な少なくとも１種のビニル系単量体単位８〜３０質量部と、を含む水系防錆塗料。
〔２〕
前記塩化ビニリデン系樹脂（１）３０〜８０質量部と、前記アクリル系樹脂（２）２０〜７０質量部と、を含み、前記塩化ビニリデン系樹脂（１）と前記アクリル合樹脂（２）との合計が、１００質量部である、前項〔１〕に記載の水系防錆塗料。
〔３〕
前記アクリル系樹脂（２）が、少なくとも１種の、カルボキシル基を有するエチレン性不飽和単量体単位と、少なくとも１種の、カルボキシル基を有しないエチレン性不飽和単量体単位と、を含む、前項〔１〕〜〔２〕いずれか１項に記載の水系防錆塗料。
〔４〕
ｐＨが、５〜９である、前項〔１〕〜〔３〕のいずれか１項に記載の水系防錆塗料。
〔５〕
前項〔１〕〜〔４〕のいずれか１項に記載の水系防錆塗料から得られる、ＡＬＣ防錆塗膜。
That is, the present invention is as follows.
[1]
The glass transition temperature (Tg) of said acrylic resin (2) is -40 degreeC or more and less than 5 degreeC including vinylidene chloride resin (1) and acrylic resin (2), and said vinylidene chloride resin (1 ) Comprises 70 to 92 parts by mass of vinylidene chloride monomer units and 8 to 30 parts by mass of at least one vinyl monomer unit copolymerizable with the vinylidene chloride monomers. .
[2]
30 to 80 parts by mass of the vinylidene chloride resin (1) and 20 to 70 parts by mass of the acrylic resin (2), and the vinylidene chloride resin (1) and the acrylic compound resin (2) The water-based anticorrosive paint according to item [1], wherein the total is 100 parts by mass.
[3]
The acrylic resin (2) includes at least one ethylenically unsaturated monomer unit having a carboxyl group and at least one ethylenically unsaturated monomer unit having no carboxyl group. The water-based anticorrosive paint according to any one of [1] to [2] above.
[4]
The water-based anticorrosive paint according to any one of [1] to [3], wherein the pH is 5 to 9.
[5]
An ALC anticorrosive coating film obtained from the water-based anticorrosive paint described in any one of [1] to [4] above.
本発明によれば、耐候性、密着性、及び防錆性に優れる塗膜を形成でき、低温塗装作業性に優れる水系防錆塗料及びＡＬＣ防錆塗膜を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the coating film which is excellent in a weather resistance, adhesiveness, and rust prevention property can be formed, and the water-system rust prevention coating material and ALC rust prevention coating film which are excellent in low-temperature coating workability | operativity can be provided.
以下、本発明を実施するための形態（以下、「本実施形態」という。）について詳細に説明するが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。 DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.
〔水系防錆塗料〕
本実施形態に係る水系防錆塗料は、
塩化ビニリデン系樹脂（１）とアクリル系樹脂（２）とを含み、前記アクリル系樹脂（２）のガラス転移温度（Ｔｇ）が−４０℃以上５℃未満であり、前記塩化ビニリデン系樹脂（１）が、塩化ビニリデン単量体単位７０〜９２質量部と、該塩化ビニリデン単量体と共重合可能な少なくとも１種のビニル系単量体単位８〜３０質量部と、を含む。
[Water-based anti-corrosion paint]
The water-based rust preventive paint according to this embodiment is
The glass transition temperature (Tg) of said acrylic resin (2) is -40 degreeC or more and less than 5 degreeC including vinylidene chloride resin (1) and acrylic resin (2), and said vinylidene chloride resin (1 ) Includes 70 to 92 parts by mass of vinylidene chloride monomer units and 8 to 30 parts by mass of at least one vinyl monomer unit copolymerizable with the vinylidene chloride monomers.
＜塩化ビニリデン系樹脂（１）＞
本実施形態で用いる塩化ビニリデン系樹脂（１）は、塩化ビニリデン単量体と該塩化ビニリデン単量体と共重合可能なその他のビニル系単量体からなる共重合体であって、重合体を構成する全単量体単位を１００質量部として、塩化ビニリデン単量体単位７０〜９２質量部と、該塩化ビニリデン単量体と共重合可能なその他のビニル系単量体単位８〜３０質量部と、を含む。
<Vinylidene chloride resin (1)>
The vinylidene chloride resin (1) used in this embodiment is a copolymer composed of a vinylidene chloride monomer and another vinyl monomer copolymerizable with the vinylidene chloride monomer, The total monomer unit constituting 100 parts by mass, 70 to 92 parts by mass of vinylidene chloride monomer units, and 8 to 30 parts by mass of other vinyl monomer units copolymerizable with the vinylidene chloride monomer And including.
その他のビニル系単量体単位は、１種単独で用いても２種以上を併用してもよい。なお、本明細書において「単量体」とは、重合前の化合物をいい、「単量体単位」とは、単量体から導かれる樹脂中の構成単位をいう。 Other vinyl monomer units may be used alone or in combination of two or more. In this specification, “monomer” refers to a compound before polymerization, and “monomer unit” refers to a structural unit in a resin derived from the monomer.
塩化ビニリデン系樹脂（１）は、塩化ビニリデン系樹脂エマルションの状態であることが好ましい。エマルションの状態であることにより塗料化加工性がより向上する傾向にある。塩化ビニリデン系樹脂エマルションは、特に限定されないが、例えば、塩化ビニリデン系単量体と、該塩化ビニリデン単量体と共重合可能なビニル系単量体と、の混合物を乳化重合により共重合することにより得ることができる。なお、塩化ビニリデン系樹脂（１）及び乳化重合方法については後述する。 The vinylidene chloride resin (1) is preferably in the state of a vinylidene chloride resin emulsion. By being in the state of an emulsion, there is a tendency that the processability to paint is further improved. The vinylidene chloride resin emulsion is not particularly limited. For example, a copolymer of a vinylidene chloride monomer and a vinyl monomer copolymerizable with the vinylidene chloride monomer is copolymerized by emulsion polymerization. Can be obtained. The vinylidene chloride resin (1) and the emulsion polymerization method will be described later.
上記塩化ビニリデン単量体単位の含有量は、７０〜９２質量部であり、好ましくは７０〜８７質量部であり、より好ましくは７０〜８３質量部である。塩化ビニリデン単量体単位が７０質量部以上であることにより、バリア性の低下が抑制されるため、優れた防錆性が効果的に発現できる傾向にある。一方、塩化ビニリデン単量体単位の含有量が９２質量部以下であることにより、塗膜の成膜性の低下や防錆性の低下、さらには基材への密着性の低下が抑制できるばかりでなく、光や熱による塗膜の変色が抑制されるため耐候性もより向上する傾向にある。 Content of the said vinylidene chloride monomer unit is 70-92 mass parts, Preferably it is 70-87 mass parts, More preferably, it is 70-83 mass parts. When the vinylidene chloride monomer unit is 70 parts by mass or more, a decrease in barrier properties is suppressed, and thus excellent rust prevention properties tend to be effectively exhibited. On the other hand, when the content of the vinylidene chloride monomer unit is 92 parts by mass or less, it is possible to suppress a decrease in the film formability and rust prevention properties of the coating film, and further a decrease in adhesion to the substrate. In addition, since the discoloration of the coating film due to light and heat is suppressed, the weather resistance tends to be further improved.
また、ビニル系単量体単位の含有量は、８〜３０質量部であり、好ましくは１３〜３０質量部であり、より好ましくは１７〜３０質量部である。ビニル系単量体単位の含有量が８質量部以上であることにより、成膜性がより向上し基材への密着性が良くなるためより優れた防錆性が発現する傾向にある。また、光や熱による塗膜の変色がより少なくなるためより耐候性が向上する傾向にある。一方、ビニル系単量体単位の含有量が３０質量部以下であることにより、防錆性とバリア性の低下を一層防ぐことができる傾向にある。 Moreover, content of a vinyl-type monomer unit is 8-30 mass parts, Preferably it is 13-30 mass parts, More preferably, it is 17-30 mass parts. When the content of the vinyl-based monomer unit is 8 parts by mass or more, the film formability is further improved and the adhesion to the base material is improved, so that more excellent rust prevention properties tend to be exhibited. Moreover, since the discoloration of the coating film by light and heat becomes less, the weather resistance tends to be improved. On the other hand, when the content of the vinyl monomer unit is 30 parts by mass or less, the deterioration of the rust prevention property and the barrier property tends to be further prevented.
前記塩化ビニリデン単量体と共重合可能な、その他のビニル系単量体としては、特に限定されないが、例えば、アクリル酸メチル、アクリル酸プロピル、アクリル酸ブチル、メタクリル酸メチル等のエチレン系α，β−不飽和カルボン酸のアルキルエステル単量体；アクリロニトリル、メタクリロニトリル等のニトリル基を有するシアン化ビニル単量体；アクリル酸−２−ヒドロキシエチル、アクリル酸ヒドロキシプロピル、アクリル酸−４−ヒドロキシブチル、メタクリル酸−２−ヒドロキシエチル、メタクリル酸−２−ヒドロキシプロピルなどのエチレン系α，β−不飽和カルボン酸のヒドロキシアルキルエステル；アクリル酸グリシジル、メタクリル酸グリシジル等のエチレン系α，β−不飽和カルボン酸エポキシ基含有アルキルエステル；アクリルアミド等のエチレン系α，β−不飽和カルボン酸のアミド化合物；塩化ビニル、酢酸ビニル等のビニルエステル；ビニルメチルエーテル等のビニルエーテル；酢酸アリル等のアリルエステル；アリルメチルエーテル等のアリルエーテル；スチレン系化合物；アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマール酸等の不飽和カルボン酸含有ビニル系単量体が挙げられる。これらの中でもアクリル酸ブチルやメタクリル酸メチル、塩化ビニル、アクリル酸やメタクリル酸が汎用性と作業性の点から好ましい。 Other vinyl monomers that can be copolymerized with the vinylidene chloride monomer are not particularly limited. For example, ethylene α such as methyl acrylate, propyl acrylate, butyl acrylate, and methyl methacrylate, alkyl ester monomer of β-unsaturated carboxylic acid; vinyl cyanide monomer having nitrile group such as acrylonitrile, methacrylonitrile, etc .; 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxy acrylate Ethylene-based α, β-unsaturated carboxylic acid hydroxyalkyl esters such as butyl, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate; ethylene-based α, β-unsaturated glycidyl acrylate and glycidyl methacrylate Saturated carboxylic acid epoxy group-containing alkyl ester Amide compounds of ethylene-based α, β-unsaturated carboxylic acids such as acrylamide; Vinyl esters such as vinyl chloride and vinyl acetate; Vinyl ethers such as vinyl methyl ether; Allyl esters such as allyl acetate; Allyl ethers such as allyl methyl ether; Styrene Examples of such compounds include unsaturated carboxylic acid-containing vinyl monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid. Among these, butyl acrylate, methyl methacrylate, vinyl chloride, acrylic acid and methacrylic acid are preferable from the viewpoint of versatility and workability.
塩化ビニリデン系樹脂（１）の製造方法としては、特に限定されないが、例えば、ラジカル重合により製造することができる。ラジカル重合による塩化ビニリデン系樹脂（１）の製造方法としては、特に限定されないが、例えば、塊状重合、溶液重合、懸濁重合、乳化重合等が挙げられる。このなかでも、塩化ビニリデン系樹脂（１）は乳化重合により製造することが好ましい。乳化重合法を用いた製造方法では、塩化ビニリデン単量体と必要に応じて上記ビニル系単量体とを所定の範囲内で混合し、重合開始剤、界面活性剤等を添加して乳化重合することにより塩化ビニリデン系樹脂を含むエマルションを得ることができる。なお、重合開始剤、界面活性剤等の種類は特に限定されず、公知のものを用いることができる。また、この乳化重合は従来公知の方法と同様の方法で実施することができる。 Although it does not specifically limit as a manufacturing method of vinylidene chloride resin (1), For example, it can manufacture by radical polymerization. Although it does not specifically limit as a manufacturing method of vinylidene chloride resin (1) by radical polymerization, For example, block polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. are mentioned. Of these, the vinylidene chloride resin (1) is preferably produced by emulsion polymerization. In the production method using the emulsion polymerization method, the vinylidene chloride monomer and the vinyl monomer as necessary are mixed within a predetermined range, and a polymerization initiator, a surfactant and the like are added to perform emulsion polymerization. By doing so, an emulsion containing a vinylidene chloride resin can be obtained. In addition, types, such as a polymerization initiator and surfactant, are not specifically limited, A well-known thing can be used. Further, this emulsion polymerization can be carried out by a method similar to a conventionally known method.
＜アクリル系樹脂（２）＞
アクリル系樹脂（２）は、アクリル系樹脂エマルションの状態であることが好ましい。エマルションの状態であることにより塗料としての加工性がより向上する傾向にある。アクリル系樹脂エマルションは、特に限定されないが、例えば、少なくとも１種の、カルボキシル基を有するエチレン性不飽和単量体と、少なくとも１種の、カルボキシル基を有しないエチレン性不飽和単量体と、の混合物を乳化重合により共重合することにより得ることができる。なお、アクリル系樹脂（２）及び乳化重合方法については後述する方法が挙げられる。
<Acrylic resin (2)>
The acrylic resin (2) is preferably in the state of an acrylic resin emulsion. There exists a tendency for the workability as a coating material to improve more by being in the state of an emulsion. The acrylic resin emulsion is not particularly limited. For example, at least one ethylenically unsaturated monomer having a carboxyl group, and at least one ethylenically unsaturated monomer having no carboxyl group, Can be obtained by copolymerization by emulsion polymerization. In addition, the method mentioned later is mentioned about acrylic resin (2) and an emulsion polymerization method.
本実施形態で用いるアクリル系樹脂（２）のガラス転移温度（Ｔｇ）は、−４０℃以上５℃未満であり、好ましくは−３５℃以上０℃以下であり、より好ましくは−３０℃以上−５℃以下である。ガラス転移温度（Ｔｇ）が−４０℃未満であると、塩化ビニリデン系樹脂との混合膜にバリア性が出ないために十分な防錆性を発現させることが難しい。また、耐候性も低下する。一方、ガラス転移温度（Ｔｇ）が５℃以上であると、低温塗装作業性が低下するとともに基材への密着性が低下する。一方で、ガラス転移温度（Ｔｇ）が上記範囲内であることにより、防錆性、バリア性、及び耐候性、さらには低温塗装作業性が共に優れる防錆塗膜を得ることができる。ガラス転移温度（Ｔｇ）は、アクリル系樹脂（２）を構成する単量体単位の組成により制御することができる。本実施形態で用いられるアクリル系樹脂は特に限定されず、単独重合体であっても共重合体であってもよいが、樹脂物性を調節する点から共重合体であることが好ましい。 The glass transition temperature (Tg) of the acrylic resin (2) used in the present embodiment is −40 ° C. or higher and lower than 5 ° C., preferably −35 ° C. or higher and 0 ° C. or lower, and more preferably −30 ° C. or higher − 5 ° C. or lower. When the glass transition temperature (Tg) is less than −40 ° C., the barrier film does not appear in the mixed film with the vinylidene chloride resin, so that it is difficult to develop sufficient rust prevention. In addition, the weather resistance also decreases. On the other hand, when the glass transition temperature (Tg) is 5 ° C. or higher, the low-temperature coating workability is lowered and the adhesion to the substrate is lowered. On the other hand, when the glass transition temperature (Tg) is within the above range, it is possible to obtain a rust-preventing coating film having excellent rust prevention properties, barrier properties, weather resistance, and low-temperature coating workability. The glass transition temperature (Tg) can be controlled by the composition of monomer units constituting the acrylic resin (2). The acrylic resin used in the present embodiment is not particularly limited and may be a homopolymer or a copolymer, but is preferably a copolymer from the viewpoint of adjusting resin physical properties.
なお、単独重合体のＴｇは、例えばポリマーハンドブック（Ｊｏｈｎ Ｗｉｌｌｅｙ＆Ｓｏｎｓ）に記載されている値を使用することができる。共重合体のＴｇ（Ｋ：絶対温度）は、共重合体を構成する各単量体が単独重合体である場合の単独重合体のＴｇと、単量体の共重合比率（共重合体中の質量分率）より次式によって推定することが可能である。
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・
Ｔｇ：単量体１、２・・・単位を含む共重合体のＴｇ（Ｋ）
Ｗ１、Ｗ２・・：単量体１、単量体２、・・の共重合体中の質量分率
ここでＷ１＋Ｗ２＋・・＝１
Ｔｇ１、Ｔｇ２・・：単量体１、単量体２、・・が単独重合体である場合の単独重合体のＴｇ（Ｋ）
In addition, the value described in the polymer handbook (John Willy & Sons) can be used for Tg of a homopolymer, for example. The Tg (K: absolute temperature) of the copolymer is the Tg of the homopolymer when each monomer constituting the copolymer is a homopolymer, and the copolymerization ratio of the monomer (in the copolymer) Can be estimated by the following equation.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ...
Tg: Monomer 1, 2 ... Tg of copolymer containing units (K)
W1, W2...: Mass fraction in the copolymer of monomer 1, monomer 2,..., Where W1 + W2 +.
Tg1, Tg2,...: Tg (K) of homopolymer when monomer 1, monomer 2,.
計算に使用する単量体の単独重合体のＴｇ（Ｋ）は、例えばポリマーハンドブック（Ｊｏｈｎ Ｗｉｌｌｅｙ＆Ｓｏｎｓ）に記載されている値を使用することができる。以下、一部の単独重合体のＴｇを例示する。カッコ内の値が単独重合体のＴｇを示す。ポリスチレン（３７３Ｋ）、ポリメタクリル酸メチル（３７８Ｋ）、ポリメタクリル酸シクロヘキシル（３３９Ｋ）、ポリアクリル酸ブチル（２１９Ｋ）、ポリアクリル酸（３７９Ｋ）である。なお、γ−メタクリロキシプロピルトリアルコキシシラン、Ｓｉ含有化合物、分子中にビニル基、アクリロイル基あるいはメタクリロイル基などのラジカル重合性の二重結合を有しアクリル系単量体と共重合可能な界面活性剤（反応性乳化剤）はＴｇ計算に考慮しない。ここで「反応性乳化剤」の具体的な例示としては、スルホン酸基又は硫酸エステル基と重合性の不飽和二重結合を分子中に有する、いわゆる反応性乳化剤などのアニオン性界面活性剤；ポリオキシエチレンアルキルエーテルや、ポリオキシエチレンノニルフェニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン−ポリオキシプロピレンブロックコポリマー、又は前述の骨格と重合性の不飽和二重結合を分子中に有する反応性ノニオン性界面活性剤などのノニオン性界面活性剤などが挙げられる。 As the Tg (K) of the monomer homopolymer used for the calculation, for example, a value described in a polymer handbook (John Willy & Sons) can be used. Hereinafter, Tg of some homopolymers will be exemplified. The value in parentheses indicates the Tg of the homopolymer. Polystyrene (373K), polymethyl methacrylate (378K), polycyclohexyl methacrylate (339K), polybutyl acrylate (219K), and polyacrylic acid (379K). In addition, γ-methacryloxypropyltrialkoxysilane, Si-containing compound, surface active that can be copolymerized with acrylic monomer having radical polymerizable double bond such as vinyl group, acryloyl group or methacryloyl group in the molecule The agent (reactive emulsifier) is not considered in the Tg calculation. Here, specific examples of the “reactive emulsifier” include anionic surfactants such as so-called reactive emulsifiers having a sulfonic acid group or sulfate ester group and a polymerizable unsaturated double bond in the molecule; Oxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer, or the aforementioned skeleton and polymerizable unsaturated double bond in the molecule Nonionic surfactants such as reactive nonionic surfactants are included.
アクリル系樹脂（２）のＴｇは、熱分解ガスクロマトグラフィーや質量分析熱分解ガスクロマトグラフィーにより単量体単位の組成を分析し、上記式から特定することができる。 The Tg of the acrylic resin (2) can be specified from the above formula by analyzing the composition of the monomer unit by pyrolysis gas chromatography or mass spectrometry pyrolysis gas chromatography.
アクリル系樹脂（２）は、少なくとも１種の、カルボキシル基を有するエチレン性不飽和単量体単位と、少なくとも１種の、カルボキシル基を有しないエチレン性不飽和単量体単位と、を含むことが好ましい。 The acrylic resin (2) contains at least one ethylenically unsaturated monomer unit having a carboxyl group and at least one ethylenically unsaturated monomer unit having no carboxyl group. Is preferred.
カルボキシル基を有するエチレン性不飽和単量体としては、特に限定されないが、例えば、アクリル酸、メタクリル酸、イタコン酸、フマール酸、マレイン酸、及び無水マレイン酸、並びに、イタコン酸、及びマレイン酸の半エステルからなる群より選ばれる１又は２以上のエチレン性不飽和単量が挙げられる。 The ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and maleic anhydride, and itaconic acid and maleic acid. Examples thereof include one or more ethylenically unsaturated monomers selected from the group consisting of half esters.
また、カルボキシル基を有しないエチレン性不飽和単量体としては、特に限定されないが、例えば、アクリル酸エステル、メタクリル酸エステル（以下、単に「（メタ）アクリル酸エステル」ともいう。）；スチレン、ビニルトルエン等の芳香族単量体；酢酸ビニル、プロピオン酸ビニル、パーサチック酸ビニル等のビニルエステル類；（メタ）アクリロニトリル等のシアン化ビニル類；塩化ビニル、塩化ビニリデン等のハロゲン化ビニル類；ブタジエン等のジエン類；（メタ）アクリルアミド、ビニルピロリドン、（メタ）アクリル酸２−ヒドロキシエチル、Ｎ−メチロールアクリルアミド、Ｎ−ブトキシメチルアクリルアミド、アクロレイン、ジアセトン（メタ）アクリルアミド、ビニルメチルケトン、ビニルエチルケトン、ジアセトン（メタ）アクリレート、（メタ）アクリル酸アシッドホスホオキシエチル、（メタ）アクリル酸３−クロロ−２−アシッドホスホオキシプロピル、メチルプロパンスルホン酸アクリルアミド、ジビニルベンゼン、（ポリ）オキシエチレンモノ（メタ）アクリレート、（ポリ）プロピレングリコール（メタ）アクリレート、（メタ）アクリル酸アリル、（ポリ）オキシエチレンジ（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；加水分解性シラン単量体等の種々の単量体が挙げられる。 In addition, the ethylenically unsaturated monomer having no carboxyl group is not particularly limited. For example, acrylic acid ester, methacrylic acid ester (hereinafter, also simply referred to as “(meth) acrylic acid ester”); styrene, Aromatic monomers such as vinyltoluene; vinyl esters such as vinyl acetate, vinyl propionate and vinyl persicate; vinyl cyanides such as (meth) acrylonitrile; vinyl halides such as vinyl chloride and vinylidene chloride; butadiene Dienes such as; (meth) acrylamide, vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, N-methylolacrylamide, N-butoxymethylacrylamide, acrolein, diacetone (meth) acrylamide, vinylmethylketone, vinylethylketone, Diacetone (Meth) acrylate, (meth) acrylic acid phosphooxyethyl (meth) acrylate 3-chloro-2-acid phosphooxypropyl, methylpropanesulfonic acid acrylamide, divinylbenzene, (poly) oxyethylene mono (meth) acrylate, (Poly) propylene glycol (meth) acrylate, (meth) acrylic acid allyl, (poly) oxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, various monomers such as hydrolyzable silane monomer The body is mentioned.
上記（メタ）アクリル酸エステルとしては、特に限定されないが、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ドデシル等が挙げられる。 Although it does not specifically limit as said (meth) acrylic acid ester, For example, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid butyl, (meth) acrylic acid 2-ethylhexyl, (meth) Examples include cyclohexyl acrylate and dodecyl (meth) acrylate.
本実施形態で用いる（メタ）アクリル酸エステルの中でもシクロアルキル基を含有するエチレン性不飽和単量体を使用することが好ましい。シクロアルキル基を含有するエチレン性不飽和単量体としては、特に限定されないが、具体的には、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸メチルシクロヘキシル、及び（メタ）アクリル酸第３級ブチルシクロヘキシル等からなる群より選ばれる１種又は２種以上の単量体を使用することが好ましい。このなかでも、特に好ましくは、（メタ）アクリル酸シクロヘキシルである。このように、アクリル系樹脂（２）として、シクロアルキル基を有する（メタ）アクリル酸エステル単量体単位を含む共重合体を用いることにより、耐候性により優れる傾向にある。 Among the (meth) acrylic acid esters used in this embodiment, it is preferable to use an ethylenically unsaturated monomer containing a cycloalkyl group. Although it does not specifically limit as an ethylenically unsaturated monomer containing a cycloalkyl group, Specifically, (meth) acrylic acid cyclohexyl, (meth) acrylic acid methylcyclohexyl, and (meth) acrylic acid tertiary It is preferable to use one or more monomers selected from the group consisting of butylcyclohexyl and the like. Of these, cyclohexyl (meth) acrylate is particularly preferable. Thus, it exists in the tendency which is excellent in a weather resistance by using the copolymer containing the (meth) acrylic acid ester monomer unit which has a cycloalkyl group as acrylic resin (2).
本実施形態で用いるアクリル系樹脂（２）は、加水分解性シラン単量体単位を含むシリコーン変性アクリル系共重合体を含んでもよい。このようなアクリル系樹脂（２）を用いることにより、耐候性により優れる傾向にある。なお、加水分解性シラン単量体単位を含むシリコーン変性アクリル系共重合体はエマルションであることが好ましい。 The acrylic resin (2) used in the present embodiment may include a silicone-modified acrylic copolymer containing a hydrolyzable silane monomer unit. By using such an acrylic resin (2), the weather resistance tends to be more excellent. The silicone-modified acrylic copolymer containing a hydrolyzable silane monomer unit is preferably an emulsion.
加水分解性シラン単量体としては、特に限定されないが、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、ビニルトリス（β−メトキシエトキシ）シラン、ビニ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メトキシシラン、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メトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−ア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エトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン等からなる群より選ばれる１種又は２種以上の単量体を使用することが好ましい。このなかでも、特に好ましくは、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である。 The hydrolyzable silane monomer is not particularly limited. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyl It is preferable to use one or more monomers selected from the group consisting of methyldiethoxysilane and the like. Among these, γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane are particularly preferable.
加水分解性シラン単量体単位の含有量は、アクリル系樹脂（２）に使用する重合性単量体全体を１００質量部として、好ましくは０．０１〜５質量部であり、より好ましくは０．０５〜２質量部である。加水分解性シラン単量体単位の含有量が０．０１質量部以上であることにより、基材との密着性が向上するため耐候性がより向上する傾向にある。また、加水分解性シラン単量体単位の含有量が５質量部以下であることにより、塗膜の柔軟性が維持される傾向にある。 The content of the hydrolyzable silane monomer unit is preferably 0.01 to 5 parts by mass, more preferably 0, based on 100 parts by mass of the entire polymerizable monomer used in the acrylic resin (2). 0.05 to 2 parts by mass. When the content of the hydrolyzable silane monomer unit is 0.01 parts by mass or more, the adhesion to the base material is improved, so that the weather resistance tends to be further improved. Moreover, it exists in the tendency for the softness | flexibility of a coating film to be maintained because content of a hydrolysable silane monomer unit is 5 mass parts or less.
アクリル系樹脂（２）はラジカル重合により製造することができる。ラジカル重合によるアクリル系樹脂（２）の製造方法としては、特に限定されないが、例えば、塊状重合、溶液重合、懸濁重合、乳化重合等が挙げられる。このなかでも、乳化重合を用いた製造方法が好ましい。乳化重合法は従来公知の方法により行なうことができる。その代表例としては、水中にて乳化剤及び重合開始剤などの存在下で、ｐＨが４以下の状態で重合性単量体を、通常６０〜９０℃の加温下で乳化重合する方法が挙げられる。この工程は一回又は複数段回繰り返し行ってもよい。 The acrylic resin (2) can be produced by radical polymerization. Although it does not specifically limit as a manufacturing method of acrylic resin (2) by radical polymerization, For example, block polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. are mentioned. Among these, the manufacturing method using emulsion polymerization is preferable. The emulsion polymerization method can be performed by a conventionally known method. A typical example is a method in which a polymerizable monomer is emulsion-polymerized in water in the presence of an emulsifier, a polymerization initiator, and the like in water at a pH of 4 or less, usually under heating at 60 to 90 ° C. It is done. This step may be repeated once or multiple times.
本実施形態で用いる重合方法としては、単量体を一括して仕込む単量体一括仕込み法や、単量体を連続的に滴下する単量体滴下法、単量体と水と乳化剤とを予め混合乳化しておき、これらを滴下するプレエマルション法、あるいは、これらを組み合わせる方法などが挙げられる。なお、重合開始剤の使用方法は特に限定されるものではない。また、加水分解性シラン単量体の使用方法としては、加水分解性シラン単量体の縮合反応と不飽和単量体のラジカル重合を同時に、若しくは、加水分解性シランの縮合反応を先行させた後に不飽和単量体のラジカル重合を進行させる乳化重合方法、又は、不飽和単量体のラジカル重合を進行させた後に加水分解性シランの縮合反応を進行させる方法などが用いられる。 As a polymerization method used in this embodiment, a monomer batch charging method in which monomers are charged in a batch, a monomer dropping method in which monomers are continuously dropped, a monomer, water, and an emulsifier are used. Examples thereof include a pre-emulsion method in which they are mixed and emulsified in advance and then added dropwise, or a method of combining them. In addition, the usage method of a polymerization initiator is not specifically limited. In addition, as a method of using the hydrolyzable silane monomer, the condensation reaction of the hydrolyzable silane monomer and the radical polymerization of the unsaturated monomer were performed simultaneously, or the condensation reaction of the hydrolyzable silane was preceded. An emulsion polymerization method in which the radical polymerization of the unsaturated monomer proceeds later, or a method in which the condensation reaction of the hydrolyzable silane proceeds after the radical polymerization of the unsaturated monomer proceeds.
アクリル系樹脂（２）を乳化重合する際に使用する重合開始剤としては、特に限定されず、一般に用いられるラジカル開始剤を用いることができる。ラジカル重合開始剤は、熱又は還元性物質等によってラジカルを生成して重合性単量体の付加重合を起こさせるものであれば、特に限定されないが、例えば、水溶性又は油溶性の過硫酸塩、過酸化物、アゾビス化合物が挙げられる。このようなラジカル重合開始剤としては、特に限定されないが、具体的には、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、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）等が挙げられる。このなかでも、好ましくは水溶性のものである。なお、重合速度の促進や低温反応を望む場合には、重亜硫酸ナトリウム、塩化第一鉄、アスコルビン酸、ホルムアルデヒドスルホオキシレート塩等の還元剤をラジカル重合開始剤と組み合わせて用いることができる。 It does not specifically limit as a polymerization initiator used when carrying out emulsion polymerization of acrylic resin (2), The radical initiator generally used can be used. The radical polymerization initiator is not particularly limited as long as it generates radicals by heat or a reducing substance to cause addition polymerization of the polymerizable monomer. For example, a water-soluble or oil-soluble persulfate is used. , Peroxides, and azobis compounds. Such a radical polymerization initiator is not particularly limited, and specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2 2, 2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), and the like. Of these, water-soluble ones are preferable. When acceleration of the polymerization rate or a low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt or the like can be used in combination with the radical polymerization initiator.
必要に応じて乳化重合に際して、分子量調整剤を使用することができる。分子量調整剤としては、特に限定されないが、具体的には、ドデシルメルカプタン、ブチルメルカプタン等が挙げられる。分子量調整剤の使用方法は特に限定されるものではないが、分子量調整剤の使用量は全体単量体量の２％以下が好ましい。 A molecular weight modifier can be used in the emulsion polymerization as required. Although it does not specifically limit as a molecular weight modifier, Specifically, a dodecyl mercaptan, a butyl mercaptan, etc. are mentioned. Although the usage method of a molecular weight modifier is not specifically limited, The usage amount of a molecular weight modifier is preferably 2% or less of the total monomer amount.
アクリル系樹脂（２）が加水分解性シラン単量体単位を含む場合において、乳化重合終了後、得られたアクリル系樹脂（２）に成膜時に作用する硬化用触媒を添加することができる。このような硬化用触媒としては、特に限定されないが、例えば、ジブチルすずジラウレート、ジオクチルすずジラウレート、ジブチルすずジアセテート、オクチル酸すず、ラウリン酸すず、オクチル酸鉄、オクチル酸鉛、テトラブチルチタネートなどの有機酸の金属塩；ｎ−ヘキシルアミン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセンなどのアミン化合物が挙げられる。なお、これらの硬化用触媒が水溶性でない場合には、その使用に際して、乳化剤と水を用いてエマルション化しておくことが望ましい。 In the case where the acrylic resin (2) contains a hydrolyzable silane monomer unit, a curing catalyst that acts during film formation can be added to the obtained acrylic resin (2) after the completion of emulsion polymerization. The curing catalyst is not particularly limited, and examples thereof include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, iron octylate, lead octylate, and tetrabutyl titanate. Metal salts of organic acids; amine compounds such as n-hexylamine and 1,8-diazabicyclo [5,4,0] -7-undecene. In addition, when these curing catalysts are not water-soluble, it is desirable to emulsify using an emulsifier and water when using them.
〔水素イオン濃度（ｐＨ）〕
本実施形態の水系防錆塗料の水素イオン濃度（ｐＨ）は、好ましくは５以上９以下であり、より好ましくは６以上８以下であり、さらに好ましくは６．５以上７．５以下である。ｐＨが５以上であることにより、金属部に塗装した直後に発生する初期錆（フラッシュラスト）が抑制される傾向にある。一方、ｐＨが９以下であることにより、塗料を貯蔵した際の経時的な変色が抑制されるなど、貯蔵安定性の低下を抑制できる傾向にある。
[Hydrogen ion concentration (pH)]
The hydrogen ion concentration (pH) of the water-based anticorrosive paint of the present embodiment is preferably 5 or more and 9 or less, more preferably 6 or more and 8 or less, and further preferably 6.5 or more and 7.5 or less. When the pH is 5 or more, initial rust (flash last) that occurs immediately after coating the metal part tends to be suppressed. On the other hand, when the pH is 9 or less, there is a tendency that deterioration in storage stability can be suppressed, such as discoloration over time when the paint is stored.
本実施形態の水系防錆塗料のｐＨを調整する際に使用されるｐＨ調整剤としては、特に限定されないが、例えば、水酸化ナトリウム、アンモニア水、リン酸三ナトリウム、リン酸三カリウム、リン酸二ナトリウム、リン酸二カリウム、リン酸一ナトリウム、及びリン酸一カリウムなどのアルカリ金属ホスフェートなどの塩基性剤が好ましい。これらは１種単独で用いても２種以上を併用してもよい。 Although it does not specifically limit as a pH adjuster used when adjusting pH of the water-system antirust coating material of this embodiment, For example, sodium hydroxide, aqueous ammonia, trisodium phosphate, tripotassium phosphate, phosphoric acid Basic agents such as alkali metal phosphates such as disodium, dipotassium phosphate, monosodium phosphate, and monopotassium phosphate are preferred. These may be used alone or in combination of two or more.
塩化ビニリデン系樹脂（１）の含有量（固形分）は、塩化ビニリデン系樹脂（１）とアクリル系樹脂（２）との合計１００質量部として、好ましくは３０〜８０質量部であり、より好ましくは５０〜７０質量部であり、さらに好ましくは５０〜６０質量部である。また、アクリル系樹脂（２）の含有量（固形分）は、塩化ビニリデン系樹脂（１）とアクリル系樹脂（２）との合計１００質量部として、好ましくは２０〜７０質量部であり、より好ましくは３０〜５０質量部であり、さらに好ましくは４０〜５０質量部である。アクリル系樹脂（２）の含有量が２０質量部以上であることにより、基材との密着性、重ね塗り時の耐水密着性、バリア性が向上する傾向にある。一方、アクリル系樹脂（２）の含有量が７０質量部以下であることにより防錆性、バリア性の低下を一層防ぐことができる傾向にある。 The content (solid content) of the vinylidene chloride resin (1) is preferably 30 to 80 parts by mass, more preferably as a total of 100 parts by mass of the vinylidene chloride resin (1) and the acrylic resin (2). Is 50-70 mass parts, More preferably, it is 50-60 mass parts. Further, the content (solid content) of the acrylic resin (2) is preferably 20 to 70 parts by mass as a total of 100 parts by mass of the vinylidene chloride resin (1) and the acrylic resin (2), and more Preferably it is 30-50 mass parts, More preferably, it is 40-50 mass parts. When the content of the acrylic resin (2) is 20 parts by mass or more, the adhesion to the substrate, the water-resistant adhesion at the time of overcoating, and the barrier property tend to be improved. On the other hand, when the content of the acrylic resin (2) is 70 parts by mass or less, the deterioration of the rust prevention property and the barrier property tends to be further prevented.
〔その他の添加剤〕
本実施形態の水系防錆塗料及び後述する防錆塗膜は、塩化ビニリデン系樹脂（１）、及びアクリル系樹脂（２）のみで構成して、コーティング剤としてクリヤー塗膜を形成させるために使用することもできるし、必要に応じて、一般的に使用されている種々の公知成分、たとえば、成膜助剤、消泡剤、増粘剤、分散剤、防腐剤、及び、界面活性剤等の安定化剤、湿潤剤、可塑剤、フラッシュラスト防止剤、上記ｐＨ調整剤、ワックス、シリコーンオイルなどを任意に配合してもよい。また、必要に応じて、体質顔料、防錆顔料、紫外線吸収剤、着色顔料、を配合することもできる。
[Other additives]
The water-based anti-corrosion paint of this embodiment and the anti-corrosion coating described later are composed only of vinylidene chloride resin (1) and acrylic resin (2), and are used to form a clear coating as a coating agent. Various known components that are generally used, such as film forming aids, antifoaming agents, thickeners, dispersants, preservatives, and surfactants, can be used as necessary. Stabilizers, wetting agents, plasticizers, flash rust inhibitors, pH adjusting agents, waxes, silicone oils and the like may be optionally added. If necessary, extender pigments, rust preventive pigments, ultraviolet absorbers, and color pigments can also be blended.
成膜助剤としては、特に限定されないが、例えば、ジエチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、エチレングリコールモノ２−エチルヘキシルエーテル、２，２，４−トリメチル−１，３−ブタンジオールイソブチレート、グルタル酸ジイソプロピル、プロピレングリコールｎ−ブチルエーテル、ジプロピレングリコールｎ−ブチルエーテル、トリプロピレングリコールｎ−ブチルエーテル、ジプロピレングリコールメチルエーテル、トリプロピレングリコールメチルエーテルなどが挙げられる。これらの成膜助剤は、単独で配合してもよいし、又は任意に併用して配合することができる。 Although it does not specifically limit as a film-forming auxiliary agent, For example, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono 2-ethylhexyl ether, 2,2,4-trimethyl-1,3 -Butanediol isobutyrate, diisopropyl glutarate, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether and the like. These film forming aids may be blended alone or in any combination.
増粘剤としては、特に限定されないが、例えば、変性オルガノクレー、ポリビニルアルコール（部分鹸化ポリ酢酸ビニル等を含む）、メチルセルロース、ヒドロキシエチルセルロース、ポリビニルピロリドン等の高分子分散安定剤等、その他ポリエーテル系増粘剤、ポリカルボン酸系増粘剤等が挙げられる。これらの増粘剤は、単独で配合してもよいし、又は任意に併用して配合することができる。 The thickener is not particularly limited. For example, modified organoclay, polyvinyl alcohol (including partially saponified polyvinyl acetate, etc.), polymer dispersion stabilizers such as methyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, etc., and other polyethers A thickener, a polycarboxylic acid type thickener, etc. are mentioned. These thickeners may be blended singly or arbitrarily in combination.
体質顔料としては、特に限定されないが、例えば、炭酸カルシウム、硫酸バリウム、含水珪酸マグネシウム（タルク）、炭酸マグネシウム、硫酸カルシウム（石膏）、珪藻土、マイカ（雲母粉）、クレー（カオリン）、シリカ、アルミナホワイト、バライト粉、ペントナイト、リトポン等が挙げられる。これらの体質顔料は、単独で配合してもよいし、又は任意に併用して配合することができる。 The extender pigment is not particularly limited. For example, calcium carbonate, barium sulfate, hydrous magnesium silicate (talc), magnesium carbonate, calcium sulfate (gypsum), diatomaceous earth, mica (mica powder), clay (kaolin), silica, alumina Examples include white, barite powder, pentonite, and lithopone. These extender pigments may be blended singly or arbitrarily in combination.
防錆顔料としては、特に限定されないが、例えば、金属のリン酸塩、亜リン酸塩、リン珪酸塩、ホウ珪酸塩、ホウ酸塩、メタホウ酸塩、モリブデン酸塩、ポリリン酸塩などが挙げられる。これらの金属カチオンとしては、特に限定されないが、例えば、カルシウム、ストロンチウム、バリウム、亜鉛、アルミニウム、マグネシウムが挙げられる。また、防錆顔料としては、イオン交換を受けさせたシリカ（イオン交換樹脂で珪酸イオン（ＳｉＯ3-）を除去したシリカ等）、例えばカルシウム交換を受けさせたシリカ、キレート能を有するホスホン酸を含む防錆顔料、オルガノ置換ホスホン酸、又はホスホノカルボン酸の多価金属塩を含有する防錆顔料などが挙げられる。これらの防錆顔料は、単独で配合してもよいし、又は任意に併用して配合することができる。 The rust preventive pigment is not particularly limited, and examples thereof include metal phosphate, phosphite, phosphosilicate, borosilicate, borate, metaborate, molybdate, and polyphosphate. It is done. Although it does not specifically limit as these metal cations, For example, calcium, strontium, barium, zinc, aluminum, and magnesium are mentioned. Further, as the rust preventive pigment, ion-exchanged silica (such as silica from which silicate ions (SiO 3− ) have been removed by an ion exchange resin), for example, silica that has been subjected to calcium exchange, phosphonic acid having chelating ability, and the like Examples thereof include rust preventive pigments, organo-substituted phosphonic acids, and rust preventive pigments containing phosphonocarboxylic acid polyvalent metal salts. These rust preventive pigments may be blended singly or arbitrarily in combination.
着色顔料としては、特に限定されないが、例えば、白色顔料であれば、酸化亜鉛、鉛白、炭酸カルシウム、リトポン（硫化亜鉛と硫酸バリウムの混合物）、二酸化チタン、沈降性硫酸バリウム及びバライト粉等の無機顔料；ポリスチレン系共重合体粒子等の有機顔料が使用できる。また、黒色顔料であればカーボンブラック等が、赤色顔料であれば鉛丹、酸化鉄赤等が、黄色顔料であれば、黄鉛、亜鉛黄等が、青色顔料であればウルトラマリンブルー、フタロシアニン青が、緑色顔料であればフタロシアニン緑等が使用できる。これらの着色顔料は、単独で配合してもよいし、又は任意に併用して配合することができる。 The color pigment is not particularly limited. For example, if it is a white pigment, zinc oxide, lead white, calcium carbonate, lithopone (mixture of zinc sulfide and barium sulfate), titanium dioxide, precipitated barium sulfate, barite powder, etc. Inorganic pigments: Organic pigments such as polystyrene copolymer particles can be used. Carbon black or the like for black pigments, red lead or iron oxide red for red pigments, yellow lead or zinc yellow for yellow pigments, ultramarine blue or phthalocyanine for blue pigments If blue is a green pigment, phthalocyanine green or the like can be used. These color pigments may be blended singly or arbitrarily in combination.
紫外線吸収剤にとしては、特に限定されないが、例えば、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、トリアジン系化合物が挙げられる。ベンゾフェノン系化合物としては、特に限定されないが、例えば、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルホン酸、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２−ヒドロキシ４−ｎ−ドデシルオキシベンゾフェノン、２−ヒドロキシ−４−ベンジルオキシベンゾフェノン、ビス（５−ベンゾイル−４−ヒドロキシ−２−メトキシフェニル）メタン、２，２’−ジヒドロキシ−４，４’ジメトキシベンゾフェノン、２，２’，４’−テトラヒドロキシベンゾフェノン、４−ドデシルオキシ−２−ヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−２’−カルボキシベンゾフェノン、２−ヒドロキシ−４−ステアリルオキシベンゾフェノンなどが挙げられる。 Although it does not specifically limit as a ultraviolet absorber, For example, a benzophenone type compound, a benzotriazole type compound, and a triazine type compound are mentioned. Although it does not specifically limit as a benzophenone series compound, For example, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- methoxy benzophenone-5-sulfonic acid, 2-hydroxy-4-n -Octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy- 4,4′dimethoxybenzophenone, 2,2 ′, 4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-stearyl Such oxy benzophenone.
ベンゾトリアゾール系化合物としては、特に限定されないが、例えば、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３，５’−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３，５’−ジ−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾール、２−〔２’−ヒドロキシ−３，５’−ビス（α，α’−ジメチルベンジル）フェニル〕ベンゾトリアゾール、メチル−３−〔３−ｔｅｒｔ−ブチル−５−（２Ｈ−ベンゾトリアゾール−２−イル）−４−ヒドロキシフェニル〕プロピオネートとポリエチレングリコール（分子量３００）との縮合物（ＢＡＳＦジャパン株式会社製、製品名：ＴＩＮＵＶＩＮ１１３０）、イソオクチル−３−〔３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル〕プロピオネート（ＢＡＳＦジャパン株式会社製、製品名：ＴＩＮＵＶＩＮ３８４）、２−（３−ドデシル−５−メチル−２−ヒドロフェニル）ベンゾトリアゾール（ＢＡＳＦジャパン株式会社製、製品名：ＴＩＮＵＶＩＮ５７１）、２−（２’−ヒドロキシ−３’−ｔｅｒｔ−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−アミルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−４’−オクトキシフェニル）ベンゾトリアゾール、２−〔２’−ヒドロキシ−３’−（３”，４”，５”，６”−テトラヒドロフタルイミドメチル）−５’−メチルフェニル〕ベンゾトリアゾール、２，２−メチルレンビス〔４−（１，１，３，３−テトラメチルブチル−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール〕、２，２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ビス（１−メチル−１−フェノールエチル）フェノール（ＢＡＳＦジャパン株式会社製、製品名：ＴＩＮＵＶＩＮ９００）などが挙げられる。 Although it does not specifically limit as a benzotriazole type compound, For example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3,5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3) , 5′-di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3,5′-bis (α, α′-dimethylbenzyl) phenyl] benzotriazole, methyl-3- [3-tert -Butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate And polyethylene glycol (molecular weight 300) condensate (BASF Japan, product name: TINUVIN 1130), isooctyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4- Hydroxyphenyl] propionate (manufactured by BASF Japan, product name: TINUVIN 384), 2- (3-dodecyl-5-methyl-2-hydrophenyl) benzotriazole (manufactured by BASF Japan, product name: TINUVIN 571), 2- (2′-hydroxy-3′-tert-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-4′-octoxif Nyl) benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methyllenbis [4 -(1,1,3,3-tetramethylbutyl-6- (2H-benzotriazol-2-yl) phenol], 2,2- (2H-benzotriazol-2-yl) -4,6-bis ( 1-methyl-1-phenolethyl) phenol (manufactured by BASF Japan Ltd., product name: TINUVIN900).
トリアジン系化合物としては、特に限定されないが、例えば、２−（４，６−ビス（２，４‘−ジメチルフェニル）−１，３，５−トリアジン−２−イル）−５−ヒドロキシフェニル, とオキシラン〔（Ｃ１０―Ｃ１６主としてＣ１２−Ｃ１３アルキルオキシ）メチル〕オキシランとの反応生成物と１−メトキシ−２−プロパノール（ＢＡＳＦジャパン株式会社製、製品名：ＴＩＮＵＶＩＮ４００）、２−（２，４−ジヒドロキシフェニル）−４，６−ビス−（２，４−ジメチルフェニル）−１，３，５−トリアジンと（２−エチルヘキシル）−グリシド酸エステルの反応生成物（ＢＡＳＦジャパン株式会社製、製品名：ＴＩＮＵＶＩＮ４０５）、２，４−〔ビス２−ヒドロキシ−４−ブトキシフェニル〕−６−（２，４−ジブトキシフェニル)−１，３，５−トリアジン （ＢＡＳＦジャパン株式会社製、製品名：ＴＩＮＵＶＩＮ４６０）、ヒドロキシフェニルトリアジン（ＢＡＳＦジャパン株式会社製、製品名：ＴＩＮＵＶＩＮ４７７−ＤＷ、ＴＩＮＵＶＩＮ４７９）が挙げられる。これらの紫外線吸収剤は、単独で配合してもよいし、又は任意に併用して配合することができる。 Although it does not specifically limit as a triazine type compound, For example, 2- (4,6-bis (2,4'- dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl, and Reaction product of oxirane [(C10-C16 mainly C12-C13 alkyloxy) methyl] oxirane and 1-methoxy-2-propanol (manufactured by BASF Japan, product name: TINUVIN400), 2- (2,4-dihydroxy Reaction product of (phenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester (manufactured by BASF Japan Ltd., product name: TINUVIN405) ), 2,4- [bis-2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxypheny ) -1,3,5-triazine (BASF Japan Ltd., trade name: TINUVIN460), hydroxyphenyl triazines (BASF Japan Ltd., trade name: TINUVIN477-DW, TINUVIN479) and the like. These ultraviolet absorbers may be blended singly or arbitrarily in combination.
〔ＡＬＣ防錆塗膜〕
本実施形態のＡＬＣ防錆塗膜は、上記水系防錆塗料から得られる。本実施形態の水系防錆塗料から防錆塗膜を形成する方法には特に制限はないが、本技術分野において従来公知、又は好適に用いられている方法（例えば刷毛塗り、スプレー塗装、ローラー塗装、浸漬塗装、静電塗装、電着塗装）を、適宜使用することができる。
[ALC anti-rust coating]
The ALC rust preventive coating film of this embodiment is obtained from the water-based rust preventive paint. There is no particular limitation on the method for forming the rust-preventing coating film from the water-based rust-preventive coating material of the present embodiment, but a conventionally known or suitably used method in this technical field (for example, brush coating, spray coating, roller coating). Dip coating, electrostatic coating, electrodeposition coating) can be used as appropriate.
〔用途〕
本実施形態において、水性防錆塗料を用いて防錆塗膜を設けるべき物品としては、特に限定されないが、例えば、建築及び建材などの各種金属部材を始めとする、本技術分野において従来好適に防錆塗膜が適用されている物品に、適宜適用することができる。このなかでも、特にＡＬＣ木口の金属部防錆塗膜として好適に用いることができる。
[Use]
In the present embodiment, the article to be provided with a rust-prevention coating using a water-based rust-prevention paint is not particularly limited, but for example, conventionally suitable in this technical field, including various metal members such as construction and building materials. The present invention can be appropriately applied to articles to which a rust preventive coating is applied. Among these, it can be suitably used particularly as a metal part rust preventive coating film of an ALC wooden mouth.
以下、実施例等により本実施形態を更に具体的に説明するが、本実施形態はこれらの実施例等により何ら限定されるものではない。なお、実施例及び比較例中の部及び％は、別途の記載がないかぎりそれぞれ質量部、及び質量％を示す。 Hereinafter, the present embodiment will be described more specifically with reference to examples, but the present embodiment is not limited to these examples. In addition, unless otherwise indicated, the part and% in an Example and a comparative example show a mass part and mass%, respectively.
＜Ｔｇの測定方法＞
アクリル系共重合樹脂のＴｇは、各単量体単位の単独重合体のＴｇと、各単量体単位の共重合対中の質量分率に基づいて、下記式により算出した。
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・
Ｔｇ：単量体１、２・・・単位を含む共重合体のＴｇ（Ｋ）
Ｗ１、Ｗ２・・：単量体１、単量体２、・・の共重合体中の質量分率
ここでＷ１＋Ｗ２＋・・＝１
Ｔｇ１、Ｔｇ２・・：単量体１、単量体２、・・が単独重合体である場合の単独重合体のＴｇ（Ｋ）
<Measurement method of Tg>
The Tg of the acrylic copolymer resin was calculated by the following formula based on the Tg of the homopolymer of each monomer unit and the mass fraction in the copolymerization pair of each monomer unit.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ...
Tg: Monomer 1, 2 ... Tg of copolymer containing units (K)
W1, W2...: Mass fraction in the copolymer of monomer 1, monomer 2,..., Where W1 + W2 +.
Tg1, Tg2,...: Tg (K) of homopolymer when monomer 1, monomer 2,.
＜固形分率の測定＞
塩化ビニリデン系共重合樹脂及びアクリル系共重合樹脂の固形分率をＣＥＭ社製 水分固形分計ＳＭＡＲＴ Ｓｙｓｔｅｍ５にて測定した。
<Measurement of solid content>
The solid content rate of the vinylidene chloride copolymer resin and the acrylic copolymer resin was measured with a moisture solid content meter SMART System 5 manufactured by CEM.
＜ｐＨの測定＞
得られた樹脂エマルション及び防錆塗料のｐＨを東亜デーケーケー株式会社製のガラス電極式水素イオン濃度指示計ＨＭ−５０Ｇにて液温が２０℃の条件で測定した。
<Measurement of pH>
The pH of the obtained resin emulsion and rust preventive paint was measured with a glass electrode type hydrogen ion concentration indicator HM-50G manufactured by Toa DKK Corporation under the condition of a liquid temperature of 20 ° C.
［低温塗装作業性試験］
５℃雰囲気下にて、予め５℃に冷却されたＡＬＣ木口面に刷毛を用いて水性防錆塗料を乾燥塗膜の厚みが約１〜２ｍｍとなるように塗装した。塗膜を乾燥させた後、塗膜の表面状態を観察した。なお低温塗装作業性の評価は下記の基準とした。
○（合格） ；乾燥塗膜に割れの発生がなく、塗膜がＡＬＣ木口面に十分密着している。
△（準合格）；乾燥塗膜に割れの発生はないが、塗膜がＡＬＣ木口面から部分的にはく離している。
×（不合格）；乾燥塗膜に割れが発生し、塗膜がＡＬＣ木口面から完全にはく離している。
[Low-temperature paint workability test]
In an atmosphere of 5 ° C., a water-based anti-corrosion paint was applied to the ALC tip which had been cooled to 5 ° C. in advance using a brush so that the thickness of the dried coating film was about 1 to 2 mm. After the coating film was dried, the surface state of the coating film was observed. The low-temperature coating workability was evaluated according to the following criteria.
○ (Accepted): No cracking occurred in the dried coating film, and the coating film was sufficiently adhered to the ALC top.
Δ (semi-acceptance): Although there was no cracking in the dried coating film, the coating film was partially detached from the ALC top.
X (failed): Cracks were generated in the dried coating film, and the coating film was completely separated from the ALC top.
［耐候性試験］
鋼板（寸法：７０×１５０×１ｔ）の表裏面及び端部に、乾燥塗膜が４０μｍとなるように、アプリケーターを用いて水性防錆塗料を塗装した。得られた塗装板を２０℃、５５％ＲＨ雰囲気下、７日間乾燥した。このようにして得られた塗装板に対し、サンシャインウエザオメーター（スガ試験機株式会社製、ＷＥＬ−ＳＵＮ−ＤＣ）を用いて、曝露試験（降雨サイクル；１８分／２時間、ブラックパネル温度６０〜６５℃）を実施した。暴露前と曝露時間１００時間後の塗装板の色差（ΔＥ）を日本電色工業株式会社製色差計３００Ａにて測定した。なお、耐候性の評価は下記の基準とした。
○（合格） ；色差が１０未満
×（不合格）；色差が１０以上
[Weather resistance test]
A water-based anticorrosive paint was applied to the front and back surfaces and end portions of a steel plate (dimensions: 70 × 150 × 1 t) using an applicator so that the dry coating film became 40 μm. The obtained coated plate was dried for 7 days in an atmosphere of 20 ° C. and 55% RH. An exposure test (rain cycle; 18 minutes / 2 hours, black panel temperature 60) using a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd., WEL-SUN-DC) on the coated plate thus obtained. ~ 65 ° C). The color difference (ΔE) of the painted plate before exposure and after 100 hours of exposure was measured with a color difference meter 300A manufactured by Nippon Denshoku Industries Co., Ltd. The weather resistance was evaluated according to the following criteria.
○ (pass); color difference is less than 10 × (fail); color difference is 10 or more
［防錆性試験］
鉄筋が埋め込まれたＡＬＣ木口面に刷毛を用いて水性防錆塗料を乾燥塗膜の厚みが約１〜２ｍｍとなるように塗装し、２０℃にて５５％ＲＨ雰囲気下、７日間乾燥させた。その後、２０℃の水に７日間浸漬し、浸漬後の鉄筋部の錆発生状況を観察した。なお、防錆性の評価は下記の基準とした。
○（合格） ；錆による変色なし
△（準合格）；部分的に錆による変色あり
×（不合格）；全面に錆による変色あり
[Rust prevention test]
Aqueous anti-corrosion paint was applied to the surface of the ALC wood with embedded reinforcing bars using a brush so that the thickness of the dry coating film was about 1 to 2 mm, and dried at 20 ° C. in a 55% RH atmosphere for 7 days. . Then, it was immersed in 20 degreeC water for 7 days, and the rust generation | occurrence | production state of the reinforcement part after immersion was observed. The evaluation of rust resistance was based on the following criteria.
○ (Pass): No discoloration due to rust △ (Semi-acceptance); Partial discoloration due to rust × (Fail): Discoloration due to rust on the entire surface
［密着性試験］
鉄筋が埋め込まれたＡＬＣ木口面に刷毛を用いて水性防錆塗料を乾燥塗膜の厚みが約１〜２ｍｍとなるように２０℃雰囲気下にて塗装し、２０℃にて５５％ＲＨ雰囲気下、７日間乾燥させた。その後、−２０℃雰囲気下に１ヶ月静置し、静置後の乾燥塗膜の表面状態を観察した。
○（合格） ；乾燥塗膜に割れやはく離の発生がなく、塗膜がＡＬＣ木口面に十分密着している。
△（準合格）；乾燥塗膜に割れの発生はないが、塗膜がＡＬＣ木口面から部分的にはく離している。
×（不合格）；乾燥塗膜に割れが発生し、塗膜がＡＬＣ木口面から完全にはく離している。
[Adhesion test]
Apply a water-based anti-corrosion paint in a 20 ° C atmosphere so that the thickness of the dry coating film is about 1 to 2 mm using a brush on the ALC wood end where the reinforcing bar is embedded, and in a 55% RH atmosphere at 20 ° C. , Dried for 7 days. Then, it left still for one month in -20 degreeC atmosphere, and the surface state of the dried coating film after standing was observed.
○ (Accepted): The dried coating film was not cracked or peeled off, and the coating film was sufficiently adhered to the ALC top.
Δ (semi-acceptance): Although there was no cracking in the dried coating film, the coating film was partially detached from the ALC top.
X (failed): Cracks were generated in the dried coating film, and the coating film was completely separated from the ALC top.
＜塩化ビニリデン系共重合樹脂エマルションの合成＞
［塩化ビニリデン系共重合樹脂エマルション ＶＤ−ａ］
ガラスライニングを施した耐圧反応器中に水１００部、ドデシルベンゼンスルホン酸ソーダ０．２０部、過硫酸ナトリウム０．１部を仕込み、脱気を行った後、内容物の温度を５５℃に保った。別の容器に塩化ビニリデン８５部、塩化ビニル１０部、及びアクリル酸メチル５部を計量混合して単量体混合物を調製した。該単量体混合物のうち２部を上記耐圧反応器中に一括添加し、内圧が降下するまで重合した。続いて、単量体混合物９８部を１２時間にわたって連続的に定量圧入した。並行して、アルキルスルホン酸ソーダ１．０部も１０時間にわたって連続的に定量圧入した。この間、内容物を５５℃に保ち、内圧が十分に降下するまで反応を進行させたのち室温冷却した。かくして得られたラテックスに１５％アルキルスルホン酸ソーダ水溶液を加えて、２０℃における表面張力が４２ｍＮ／ｍとなるように調整した。この後、エバポレーターに移し６０℃に加温して未反応単量体を除去したのち室温まで冷却した。その後に樹脂固形分を５０％に調整して塩化ビニリデン系共重合樹脂エマルション〔ＶＤ−ａ〕を得た。
<Synthesis of vinylidene chloride copolymer resin emulsion>
[Vinylidene chloride copolymer resin emulsion VD-a]
100 parts of water, 0.20 part of sodium dodecylbenzenesulfonate and 0.1 part of sodium persulfate were charged into a pressure-lined reactor with glass lining, and after degassing, the temperature of the contents was maintained at 55 ° C. It was. In a separate container, 85 parts of vinylidene chloride, 10 parts of vinyl chloride, and 5 parts of methyl acrylate were weighed and mixed to prepare a monomer mixture. Two parts of the monomer mixture were added all at once into the pressure-resistant reactor and polymerized until the internal pressure dropped. Subsequently, 98 parts of the monomer mixture was metered in continuously over 12 hours. In parallel, 1.0 part of sodium alkyl sulfonate was continuously metered in over 10 hours. During this time, the contents were kept at 55 ° C., and the reaction was allowed to proceed until the internal pressure sufficiently decreased, followed by cooling at room temperature. A 15% sodium alkyl sulfonate aqueous solution was added to the latex thus obtained to adjust the surface tension at 20 ° C. to 42 mN / m. Then, it moved to the evaporator and heated at 60 degreeC, after removing the unreacted monomer, it cooled to room temperature. Thereafter, the resin solid content was adjusted to 50% to obtain a vinylidene chloride copolymer resin emulsion [VD-a].
［塩化ビニリデン系共重合樹脂エマルション ＶＤ−ｂ］
ガラスライニングを施した耐圧反応器中に水１００部、ラウリル硫酸ナトリウム０．６０部、過硫酸カリウム０．０１部を仕込み、脱気を行った後、内容物の温度を４５℃に保った。別の容器に塩化ビニリデン５０部、アクリル酸エチル５０部、を計量混合して単量体混合物を調製した。該単量体混合物のうち２０部を上記耐圧反応器中に一括添加し、内圧が降下するまで重合した。続いて、単量体混合物８０部を２０時間にわたって連続的に定量圧入した。並行して、過硫酸カリウム０．０２部、無水重亜硫酸ソーダ０．０１部、ラウリル硫酸ナトリウム２．０部も２０時間にわたって連続的に定量圧入した。この間、内容物を４５℃に保ち、内圧が十分に降下するまで反応を進行させたのち室温冷却した。かくして得られたラテックスに３０％ラウリル硫酸ナトリウム水溶液を加えて、２０℃における表面張力が４２ｍＮ／ｍとなるように調整した。この後、エバポレーターに移し６０℃に加温して未反応単量体を除去したのち室温まで冷却した。その後に樹脂固形分を５０％に調整して塩化ビニリデン系共重合樹脂エマルション〔ＶＤ−ｂ〕を得た。
[Vinylidene chloride copolymer resin emulsion VD-b]
100 parts of water, 0.60 part of sodium lauryl sulfate, and 0.01 part of potassium persulfate were charged into a pressure-resistant reactor with glass lining, and after degassing, the temperature of the contents was kept at 45 ° C. In a separate container, 50 parts of vinylidene chloride and 50 parts of ethyl acrylate were weighed and mixed to prepare a monomer mixture. 20 parts of the monomer mixture was added all at once into the pressure-resistant reactor and polymerized until the internal pressure dropped. Subsequently, 80 parts of the monomer mixture was continuously metered in over 20 hours. In parallel, 0.02 part of potassium persulfate, 0.01 part of anhydrous sodium bisulfite and 2.0 parts of sodium lauryl sulfate were continuously metered in over 20 hours. During this time, the contents were kept at 45 ° C., and the reaction was allowed to proceed until the internal pressure sufficiently decreased, followed by cooling at room temperature. A 30% aqueous sodium lauryl sulfate solution was added to the latex thus obtained to adjust the surface tension at 20 ° C. to 42 mN / m. Then, it moved to the evaporator and heated at 60 degreeC, after removing the unreacted monomer, it cooled to room temperature. Thereafter, the resin solid content was adjusted to 50% to obtain a vinylidene chloride copolymer resin emulsion [VD-b].
＜アクリル系共重合樹脂エマルションの合成＞
［アクリル系共重合樹脂エマルション ＡＣ−ａ］
ステンレス製容器にスチレン４１部、アクリル酸２エチルヘキシル５５部、メタクリル酸４部、エマルゲン１５０（花王（株）製、ポリオキシエチレンアルキルエーテル）の２０％水溶液４部、過硫酸アンモニウムの２％水溶液０．４部、水６２部を添加し、ホモミキサーにより５分間混合してプレ乳化液を作製した。
<Synthesis of acrylic copolymer resin emulsion>
[Acrylic copolymer resin emulsion AC-a]
In a stainless steel container, 41 parts of styrene, 55 parts of 2-ethylhexyl acrylate, 4 parts of methacrylic acid, 4 parts of 20% aqueous solution of Emulgen 150 (manufactured by Kao Corporation, polyoxyethylene alkyl ether), 2% aqueous solution of ammonium persulfate 4 parts and 62 parts of water were added and mixed with a homomixer for 5 minutes to prepare a pre-emulsion solution.
撹拌機、還流冷却器、滴下槽及び温度計を取りつけた反応容器に、エマールＤ−３−Ｄ（花王（株）製、ポリオキシエチレンアルキルエーテル硫酸ナトリウム）の２５％水溶液０．０６部、エマルゲン１４７（花王（株）製、ポリオキシエチレンラウリルエーテル）０．２５部、エマルゲン１５０（花王（株）製、ポリオキシエチレンアルキルエーテル）０．５部、水５７部を仕込み、反応器内の温度を８０℃保ったまま、過硫酸アンモニウムの２％水溶液を０．０２５部添加した。添加した５分後に上記プレ乳化液を１２０分かけて一定流速で滴下した。反応容器温度を８０℃に保ったまま６０分維持した。その後冷却し、１０％濃度のアンモニア水溶液を添加してｐＨ８に調整したのちアクリル系樹脂エマルション〔ＡＣ−ａ〕を得た。得られたエマルションのガラス転移温度（Ｔｇ）は−１５℃、固形分は４５％であった。 In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 0.06 part of 25% aqueous solution of Emar D-3-D (manufactured by Kao Corporation, sodium polyoxyethylene alkyl ether sulfate), Emulgen 147 (manufactured by Kao Corporation, polyoxyethylene lauryl ether) 0.25 part, Emulgen 150 (manufactured by Kao Corporation, polyoxyethylene alkyl ether) 0.5 part, 57 parts of water were charged, and the temperature in the reactor Was kept at 80 ° C., and 0.025 part of a 2% aqueous solution of ammonium persulfate was added. Five minutes after the addition, the pre-emulsion was dropped at a constant flow rate over 120 minutes. The reaction vessel temperature was maintained at 80 ° C. for 60 minutes. Thereafter, the mixture was cooled, and an aqueous ammonia solution having a concentration of 10% was added to adjust the pH to 8. After that, an acrylic resin emulsion [AC-a] was obtained. The obtained emulsion had a glass transition temperature (Tg) of −15 ° C. and a solid content of 45%.
［アクリル系共重合樹脂エマルション ＡＣ−ｂ］
ステンレス製容器にメタクリル酸メチル１８部、アクリル酸ブチル８０部、メタクリル酸１部、アクリル酸メチル１部、エマールＤ−３−Ｄ（花王（株）製、ポリオキシエチレンアルキルエーテル硫酸ナトリウム）の２５％水溶液１．０５部、ラムテルＥ−１１８Ｂ（花王（株）製、ポリオキシエチレンアルキルエーテル硫酸ナトリウム）２．４部、過硫酸アンモニウムの２％水溶液０．２部、水４０部を添加し、ホモミキサーにより５分間混合してプレ乳化液を作製した。
[Acrylic copolymer resin emulsion AC-b]
25 parts of 18 parts of methyl methacrylate, 80 parts of butyl acrylate, 1 part of methacrylic acid, 1 part of methyl acrylate, Emar D-3-D (manufactured by Kao Corporation, sodium polyoxyethylene alkyl ether sulfate) in a stainless steel container % Aqueous solution 1.05 part, Ramtel E-118B (manufactured by Kao Corporation, polyoxyethylene alkyl ether sodium sulfate) 2.4 part, 2% aqueous solution of ammonium persulfate 0.2 part, water 40 parts were added. A pre-emulsion was prepared by mixing for 5 minutes with a mixer.
撹拌機、還流冷却器、滴下槽及び温度計を取りつけた反応容器に、水６３部を仕込み、反応器内の温度を８０℃保ったまま、過硫酸アンモニウムの２％水溶液を０．０６部添加した。添加した５分後に上記プレ乳化液を１２０分かけて一定流速で滴下した。反応容器温度を８０℃に保ったまま６０分維持し、その後室温まで冷却し、アクリル系樹脂エマルション〔ＡＣ−ｂ〕を得た。得られたエマルションのガラス転移温度（Ｔｇ）は−３４℃、固形分は４５％であった。 A reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer was charged with 63 parts of water, and 0.06 part of a 2% aqueous solution of ammonium persulfate was added while maintaining the temperature in the reactor at 80 ° C. . Five minutes after the addition, the pre-emulsion was dropped at a constant flow rate over 120 minutes. The reaction vessel temperature was maintained at 80 ° C. for 60 minutes and then cooled to room temperature to obtain an acrylic resin emulsion [AC-b]. The obtained emulsion had a glass transition temperature (Tg) of −34 ° C. and a solid content of 45%.
［アクリル系共重合樹脂エマルション ＡＣ−ｃ］
ステンレス製容器にメタクリル酸メチル４３部、メタクリル酸シクロヘキシル２０部、アクリル酸ブチル３５部、アクリル酸２部、「アクアロンＫＨ−１０２５」６．０部、ノニオン性乳化剤「エマルゲン１２０」（商品名、花王（株）製）の２０％水溶液１．５部、過硫酸アンモニウムの２％水溶液８．５部、γ−メタクリロキシプロピルトリメトキシシラン０．２５部、水７０部をホモジナイザーにより５分間混合してプレ乳化液を作製した。
[Acrylic copolymer resin emulsion AC-c]
In a stainless steel container, 43 parts of methyl methacrylate, 20 parts of cyclohexyl methacrylate, 35 parts of butyl acrylate, 2 parts of acrylic acid, 6.0 parts of “Aqualon KH-1025”, nonionic emulsifier “Emulgen 120” (trade name, Kao) 1.5 parts of 20% aqueous solution, 8.5 parts of 2% aqueous solution of ammonium persulfate, 0.25 part of γ-methacryloxypropyltrimethoxysilane, and 70 parts of water were mixed for 5 minutes with a homogenizer. An emulsion was prepared.
撹拌機、還流冷却器、滴下槽及び温度計を取りつけた反応容器に、水５０部とアニオン性反応性乳化剤「アクアロンＫＨ−１０２５」（登録商標、第一工業製薬（株）製、２５％水溶液）０．８部仕込み、反応器内の温度を８０℃保ったまま、過硫酸アンモニウムの２％水溶液を１．５部添加した。添加した５分後に上記プレ乳化液を２００分かけて一定流速で滴下した。反応容器温度を８０℃に保ったまま６０分維持し、その後室温まで冷却し、アクリル系樹脂エマルション〔ＡＣ−ｃ〕を得た。得られたエマルションのガラス転移温度（Ｔｇ）は２３℃、固形分は４６％であった。 In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 50 parts of water and an anionic reactive emulsifier “AQUALON KH-1025” (registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 25% aqueous solution) ) 0.8 parts were charged, and 1.5 parts of a 2% aqueous solution of ammonium persulfate was added while maintaining the temperature in the reactor at 80 ° C. Five minutes after the addition, the pre-emulsion was dropped at a constant flow rate over 200 minutes. The reaction vessel temperature was maintained at 80 ° C. for 60 minutes and then cooled to room temperature to obtain an acrylic resin emulsion [AC-c]. The obtained emulsion had a glass transition temperature (Tg) of 23 ° C. and a solid content of 46%.
［アクリル系共重合樹脂エマルション ＡＣ−ｄ］
ステンレス製容器にメタクリル酸メチル１０部、アクリル酸ブチル７０部、アクリル酸２エチルヘキシル２０部、エマールＤ−３−Ｄ（花王（株）製、ポリオキシエチレンアルキルエーテル硫酸ナトリウム）の２５％水溶液１．０５部、ラムテルＥ−１１８Ｂ（花王（株）製、ポリオキシエチレンアルキルエーテル硫酸ナトリウム）２．４部、過硫酸アンモニウムの２％水溶液０．２部、水４０部を添加し、ホモミキサーにより５分間混合してプレ乳化液を作製した。
[Acrylic copolymer resin emulsion AC-d]
1. A 25% aqueous solution of 10 parts of methyl methacrylate, 70 parts of butyl acrylate, 20 parts of 2-ethylhexyl acrylate, Emar D-3-D (manufactured by Kao Corporation, sodium polyoxyethylene alkyl ether sulfate) in a stainless steel container 05 parts, 2.4 parts of Ramtel E-118B (manufactured by Kao Corporation, polyoxyethylene alkyl ether sodium sulfate), 0.2 part of a 2% aqueous solution of ammonium persulfate, and 40 parts of water were added, and 5 minutes by a homomixer. A pre-emulsion was prepared by mixing.
撹拌機、還流冷却器、滴下槽及び温度計を取りつけた反応容器に、水６３部を仕込み、反応器内の温度を８０℃保ったまま、過硫酸アンモニウムの２％水溶液を０．０６部添加した。添加した５分後に上記プレ乳化液を１２０分かけて一定流速で滴下した。反応容器温度を８０℃に保ったまま６０分維持し、その後室温まで冷却し、アクリル系樹脂エマルション〔ＡＣ−ｄ〕を得た。得られたエマルションのガラス転移温度（Ｔｇ）は−４８℃、固形分は４５％であった。 A reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer was charged with 63 parts of water, and 0.06 part of a 2% aqueous solution of ammonium persulfate was added while maintaining the temperature in the reactor at 80 ° C. . Five minutes after the addition, the pre-emulsion was dropped at a constant flow rate over 120 minutes. The reaction vessel temperature was maintained at 80 ° C. for 60 minutes and then cooled to room temperature to obtain an acrylic resin emulsion [AC-d]. The obtained emulsion had a glass transition temperature (Tg) of −48 ° C. and a solid content of 45%.
上記のようにして得られた塩化ビニリデン系樹脂とアクリル系樹脂について、表１に示す。 The vinylidene chloride resin and acrylic resin obtained as described above are shown in Table 1.
［実施例１］
純水８．５７部、ノプコ８０３４Ｌ（消泡剤：サンノプコ（株）製）０．１１部、エマルゲンＰＰ２９０（安定化剤：花王株式会社製）２０％水溶液２．２４部、サーフィノール１０４Ｅ（湿潤剤：日信化学工業株式会社製）０．１８部、Ｐｒｏｘｅｌ ＢＤ（防腐剤：Ａｖｅｃｉａ製）０．０３部、ＢＹＫ１５４（分散剤：ＢＹＫ Ｃｈｅｍｉｅ Ｇｍｂｈ製）０．３１部、Ｋ−ｗｈｉｔｅ８４（防錆顔料：テイカ株式会社製）５．６７部、ＪＲ−７０１（着色顔料：テイカ株式会社製）５．５部、タルクＭＳ（体質顔料：日本タルク株式会社製）６．６３部を容器に仕込み、ＶＭＡ ＧＥＴＺＭＡＮＮ ＧｍｂＨ社製 ＤＩＳＰＥＲＭＡＴ ＧＭＢＨ−Ｄ−５１５８０にて毎分１００００回転で２０分間攪拌して顔料分散液を調製した。この顔料分散液に、塩化ビニリデン系共重合樹脂エマルション〔ＶＤ−ａ〕を３３．７３部（樹脂固形分比５０）及びアクリル系共重合樹脂エマルション〔ＡＣ−ａ〕を３７．４８部（樹脂固形分比５０）、ＣＳ−１２（成膜助剤：チッソ（株）製）１．００部、１０％亜硝酸ナトリウム（フラッシュラスト防止剤：和光純薬工業（株）製）１．１４部、ＳＮデフォーマー７７７（消泡剤：サンノプコ（株）製）０．１８部、ＵＨ４２０（増粘剤：商品名、（株）ＡＤＥＫＡ製５０％水溶液）１．３０部を加えて均一なるまで攪拌して水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Example 1]
8.57 parts of pure water, Nopco 8034L (antifoaming agent: manufactured by San Nopco) 0.11 part, Emargen PP290 (stabilizer: manufactured by Kao Corporation) 2.24 parts of 20% aqueous solution, Surfynol 104E (wet) Agent: manufactured by Nissin Chemical Industry Co., Ltd.) 0.18 part, Proxel BD (preservative: manufactured by Avecia) 0.03 part, BYK154 (dispersant: manufactured by BYK Chemie GmbH), 0.31 part, K-white84 (antirust) Pigment: manufactured by Taika Co., Ltd.) 5.67 parts, JR-701 (colored pigment: manufactured by Taika Co., Ltd.) 5.5 parts, talc MS (external pigment: manufactured by Nihon Talc Co., Ltd.) 6.63 parts, A pigment dispersion was prepared by stirring for 20 minutes at 10,000 rpm in a DISPERMAT GMBH-D-51580 manufactured by VMA GETZMANN GmbH. To this pigment dispersion, 33.73 parts of vinylidene chloride copolymer resin emulsion [VD-a] (resin solid content ratio 50) and 37.48 parts of acrylic copolymer resin emulsion [AC-a] (resin solids) 50), CS-12 (film forming aid: manufactured by Chisso Corporation) 1.00 parts, 10% sodium nitrite (flash rust inhibitor: manufactured by Wako Pure Chemical Industries, Ltd.) 1.14 parts, Add SN Deformer 777 (antifoaming agent: Sannopco Co., Ltd.) 0.18 parts, UH420 (thickener: trade name, 50% aqueous solution manufactured by ADEKA Co., Ltd.) 1.30 parts and stir until uniform. A water-based anticorrosive paint was obtained. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
［実施例２］
アクリル系共重合樹脂エマルション〔ＡＣ−ａ〕に代えて、アクリル系共重合樹脂エマルション〔ＡＣ−ｂ〕を用いたこと以外は、実施例１と同様の方法で水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Example 2]
A water-based anticorrosive paint was obtained in the same manner as in Example 1 except that the acrylic copolymer resin emulsion [AC-b] was used instead of the acrylic copolymer resin emulsion [AC-a]. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
［実施例３］
塩化ビニリデン系共重合エマルション〔ＶＤ−ａ〕とアクリル系共重合樹脂エマルション〔ＡＣ−ａ〕の樹脂固形分比率が７０：３０になるように変更した以外は、実施例１と同様の方法で水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Example 3]
Except that the resin solid content ratio of the vinylidene chloride copolymer emulsion [VD-a] and the acrylic copolymer resin emulsion [AC-a] was changed to 70:30, it was aqueous in the same manner as in Example 1. An antirust paint was obtained. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
［実施例４］
塩化ビニリデン系共重合エマルション〔ＶＤ−ａ〕とアクリル系共重合樹脂エマルション〔ＡＣ−ａ〕の樹脂固形分比率が３０：７０になるように変更した以外は、実施例１と同様の方法で水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Example 4]
Except for changing the resin solid content ratio of the vinylidene chloride copolymer emulsion [VD-a] and the acrylic copolymer resin emulsion [AC-a] to be 30:70, the aqueous solution was prepared in the same manner as in Example 1. An antirust paint was obtained. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
［比較例１］
アクリル系共重合樹脂エマルション〔ＡＣ−ａ〕に代えて、アクリル系共重合樹脂エマルション〔ＡＣ−ｃ〕を用いたこと以外は、実施例１と同様の方法で水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Comparative Example 1]
A water-based anticorrosive paint was obtained in the same manner as in Example 1 except that the acrylic copolymer resin emulsion [AC-c] was used in place of the acrylic copolymer resin emulsion [AC-a]. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
［比較例２］
アクリル系共重合樹脂エマルション〔ＡＣ−ａ〕に代えて、アクリル系共重合樹脂エマルション〔ＡＣ−ｄ〕を用いたこと以外は、実施例１と同様の方法で水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Comparative Example 2]
A water-based anticorrosive paint was obtained in the same manner as in Example 1 except that the acrylic copolymer resin emulsion [AC-d] was used instead of the acrylic copolymer resin emulsion [AC-a]. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
［比較例３］
アクリル系共重合樹脂エマルション〔ＡＣ−ａ〕を用いず、塩化ビニリデン系共重合エマルション〔ＶＤ−ａ〕を樹脂固形分で１００部配合した以外は、実施例１と同様の方法で水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Comparative Example 3]
Aqueous rust preventive paint in the same manner as in Example 1 except that 100 parts of vinylidene chloride copolymer emulsion [VD-a] was blended in resin solid content without using acrylic copolymer resin emulsion [AC-a]. Got. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
［比較例４］
塩化ビニリデン系共重合エマルション〔ＶＤ−ａ〕を用いず、アクリル系共重合樹脂エマルション〔ＡＣ−ａ〕を樹脂固形分で１００部配合した以外は、実施例１と同様の方法で水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Comparative Example 4]
A water-based anticorrosive paint in the same manner as in Example 1 except that 100 parts of acrylic copolymer resin emulsion [AC-a] was blended in resin solid content without using vinylidene chloride copolymer emulsion [VD-a]. Got. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
［比較例５］
塩化ビニリデン系共重合エマルション〔ＶＤ−ｂ〕とアクリル系共重合樹脂エマルションを〔ＡＣ−ａ〕の固形分比率が５０：５０になるように変更した以外は、実施例１と同様の方法で水性防錆塗料を得た。得られた塗料を防錆塗膜にして、前記の試験を行った。その結果を表２に示す。
[Comparative Example 5]
Except for changing the vinylidene chloride copolymer emulsion [VD-b] and the acrylic copolymer resin emulsion so that the solid content ratio of [AC-a] is 50:50, the aqueous solution was prepared in the same manner as in Example 1. An antirust paint was obtained. The obtained paint was made into a rust-proof coating film and the above test was conducted. The results are shown in Table 2.
本発明の水系防錆塗料は、低温塗装作業性が良好で、各種基材への密着性、防錆性、耐候性に優れる。そのため、本発明は、ＡＬＣ木口等の金属部防錆をはじめ、各種金属部材への防錆塗料用途において好適であり、産業の各分野おいて高い利用可能性を有する。 The water-based anticorrosive paint of the present invention has good low-temperature coating workability, and is excellent in adhesion to various base materials, antirust, and weather resistance. Therefore, the present invention is suitable for use in anticorrosive paints for various metal members including metal part anticorrosion such as ALC wood ends, and has high applicability in various industrial fields.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046988A (en) * | 2016-07-27 | 2016-10-26 | 苏州明轩地坪涂料有限公司 | Matte coating |
| JP2017190451A (en) * | 2016-04-12 | 2017-10-19 | 花王株式会社 | Anionic surfactant composition for emulsion polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61221253A (en) * | 1985-03-26 | 1986-10-01 | Toagosei Chem Ind Co Ltd | Aqueous coating composition |
| JPH0952997A (en) * | 1995-08-15 | 1997-02-25 | Asahi Chem Ind Co Ltd | Acrylic emulsion |
| JP2013151598A (en) * | 2012-01-25 | 2013-08-08 | Asahi Kasei Chemicals Corp | Water-based rust-proof paint |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61221253A (en) * | 1985-03-26 | 1986-10-01 | Toagosei Chem Ind Co Ltd | Aqueous coating composition |
| JPH0952997A (en) * | 1995-08-15 | 1997-02-25 | Asahi Chem Ind Co Ltd | Acrylic emulsion |
| JP2013151598A (en) * | 2012-01-25 | 2013-08-08 | Asahi Kasei Chemicals Corp | Water-based rust-proof paint |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017190451A (en) * | 2016-04-12 | 2017-10-19 | 花王株式会社 | Anionic surfactant composition for emulsion polymerization |
| CN106046988A (en) * | 2016-07-27 | 2016-10-26 | 苏州明轩地坪涂料有限公司 | Matte coating |
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