JP4384392B2 - Process for producing emulsion composition for paint - Google Patents
Process for producing emulsion composition for paint Download PDFInfo
- Publication number
- JP4384392B2 JP4384392B2 JP2002221039A JP2002221039A JP4384392B2 JP 4384392 B2 JP4384392 B2 JP 4384392B2 JP 2002221039 A JP2002221039 A JP 2002221039A JP 2002221039 A JP2002221039 A JP 2002221039A JP 4384392 B2 JP4384392 B2 JP 4384392B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- meth
- emulsion
- polymerization
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000839 emulsion Substances 0.000 title claims description 39
- 239000003973 paint Substances 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 title claims description 12
- 238000000034 method Methods 0.000 title description 14
- 239000000178 monomer Substances 0.000 claims description 86
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 29
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000003505 polymerization initiator Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- -1 2-ethylhexyl Chemical group 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- LAGVOJJKZPIRMS-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-3-yl) 2-methylprop-2-enoate Chemical compound CN1C(C)(C)CCC(OC(=O)C(C)=C)C1(C)C LAGVOJJKZPIRMS-UHFFFAOYSA-N 0.000 description 1
- GIIUJJXXMYYQQD-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)C=C GIIUJJXXMYYQQD-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000001139 pH measurement Methods 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
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 229940001474 sodium thiosulfate Drugs 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 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 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
この発明は、塗料用エマルジョン組成物の製造方法に関する。
【０００２】
【従来の技術】
従来、建築物の内外壁材の塗装用塗料としては、水性の（メタ）アクリル系樹脂エマルジョン型塗料が使用されている。これは、この塗料が水系型塗料であるため、溶剤型塗料と比較した場合、湿潤面に直接塗布することができ、取扱いが容易であり、溶剤臭を発生せず、引火・爆発を起こす危険性が少なく、比較的安価であるという特徴を有するからである。
【０００３】
しかし、この水性の（メタ）アクリル系樹脂エマルジョン型塗料から形成される塗膜は、耐候性が不十分であり、溶剤型塗料に比べて光沢性に劣るという問題点を有する。
【０００４】
これに対し、特開平３−１２８９７８号公報や特開平５−１４０２４０号公報に、シクロアルキル基含有モノマーや重合性紫外線安定性モノマー等を原料モノマーとしてラジカル重合した塗料用樹脂組成物が開示されている。また、特開平７−１３３４５８号公報に、イソボルニル（メタ）アクリレートや光安定性付与モノマー等を原料モノマーとしてラジカル重合した塗料用樹脂組成物が開示されている。
これらの塗料用樹脂組成物は、耐候性や光沢性に優れるという特徴を有する。
【０００５】
【発明が解決しようとする課題】
しかしながら、上記の重合性紫外線安定性モノマーや光安定性付与モノマーは、ラジカルをトラップする性質を有するため、上記のラジカル重合においては、重合反応の抑制効果を発揮する。このため、大量の重合開始剤が必要となり、重合開始剤への連鎖移動が顕著となり、得られる樹脂の平均分子量が、あまり大きくできないため、得られる塗料用樹脂組成物の耐候性や光沢性は、必ずしも十分なものとはいえない場合が生じる。
【０００６】
そこで、この発明は、十分な耐候性や光沢性に優れた水系の塗料用樹脂組成物の製造方法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
この発明は、（メタ）アクリル酸系単量体を水性媒体中で第１段の乳化重合を行い、転化率が７０％以上に達した後に、重合性紫外線安定性単量体及び／又は重合性光安定性単量体を予備乳化した予備乳化液、好ましくは、これと（メタ）アクリル酸系単量体とを予備乳化した予備乳化液を添加して第２段の乳化重合を行うことにより、上記の課題を解決したのである。
【０００８】
乳化重合反応を２段階に分け、まず、第１段の乳化重合を行い、この段階の重合反応速度が高い状態のときに、重合性紫外線安定性単量体及び／又は重合性光安定性単量体を含む予備乳化液を添加して第２段目の乳化重合を行う。このため、重合性紫外線安定性単量体及び／又は重合性光安定性単量体によって重合反応が抑制されても、重合反応速度が低くなるまでには、第２段目の重合のほとんどが進行してしまい、また、重合性紫外線安定性単量体及び／又は重合性光安定性単量体も容易に重合して、重合体の中に取り込まれることとなる。
また、この第２段の乳化重合時に（メタ）アクリル酸系単量体を併せて用いることにより、上記の重合性紫外線安定性単量体及び／又は重合性光安定性単量体の重合体中への取り込みが容易となり、反応効率がさらに向上する。
【０００９】
【発明の実施の形態】
以下、この発明の実施形態を説明する。
この発明にかかる塗料用エマルジョン組成物の製造方法は、２段階の乳化重合を行う製造方法である。
【００１０】
第１段目の乳化重合は、（メタ）アクリル酸系単量体を水性媒体中で重合することにより行われる。この（メタ）アクリル酸系単量体としては、（メタ）アクリル酸アルキルエステル、シクロアルキル基を有する（メタ）アクリル酸系単量体、（メタ）アクリル酸系単量体、（メタ）アクリル酸アルコキシアルキルエステル、架橋性を有する（メタ）アクリル酸アルキルエステル等があげられ、重合に際しては、その１種を用いても、２種以上を用いてもよい。
【００１１】
上記（メタ）アクリル酸アルキルエステルとしては、（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）アクリル酸ベンジル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル等があげられる。
【００１２】
上記シクロアルキル基を有する（メタ）アクリル酸系単量体としては、（メタ）アクリル酸シクロヘキシル、イソボルニル（メタ）アクリレート等があげられる。
上記（メタ）アクリル酸系単量体としては、アクリル酸又はメタクリル酸があげられる。
【００１３】
上記（メタ）アクリル酸アルコキシアルキルエステルとしては、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸２−ブトキシエチル等があげられる。
【００１４】
上記架橋性を有する（メタ）アクリル酸アルキルエステルとしては、（メタ）アクリル酸アリル、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等があげられる。
なお、この明細書において、「（メタ）アクリル」とは、「アクリル又はメタクリル」を意味する。
【００１５】
この第１段の乳化重合法としては、特に限定がなく、通常の水性媒体中で行なわれる、例えばバッチ重合法、モノマー滴下重合法、乳化モノマー滴下重合法などの各種乳化重合法の中から適宜選択して採用することができる。この中でも、特に製造時にエマルジョンの安定性を確保するうえで、モノマー滴下重合法および乳化モノマー滴下重合法が好ましい。
【００１６】
上記水性媒体としては、水や、水にメタノール、エタノール、プロパノール等の水溶性溶媒を混合した水−水溶性溶媒混合液等があげられる。この中でも、水が特に好ましい。
【００１７】
この第１段の乳化重合において使用される重合開始剤としては、通常の乳化重合で使用される重合開始剤を使用することができる。この重合開始剤の例としては、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の過硫酸塩、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ化合物、過酸化水素、ｔ−ブチルハイドロパーオキサイド等のハイドロパーオキサイド類、ベンゾイルパーオキサイド、ラウロイルパーオキサイド等の過酸化物等のラジカル重合開始剤があげられ、これらは単独でまたは２種以上を混合して用いることができる。また、これらラジカル重合開始剤と、例えば亜硫酸ナトリウム、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、酒石酸、Ｌ−アスコルビン酸などの還元剤とを併用してレドックス系重合開始剤として用いることもできる。
【００１８】
この乳化重合の際には、エマルジョンの安定性を向上させるために、乳化剤を用いることができる。この乳化剤としては、通常乳化重合に用いられるものであればとくに限定がなく、例えば、アニオン性、カチオン性、両イオン性等のイオン性界面活性剤、ノニオン性界面活性剤などがあげられる。
【００１９】
上記乳化重合時の反応液は、重合の安定性の面から、たとえばアンモニア水などのｐＨ調整剤を乳化重合時に使用することによってｐＨを調整することができる。また、反応温度は、通常５０〜１００℃程度、反応時間は、通常２〜１６時間程度とすることが好ましい。
【００２０】
次に、第２段目の乳化重合は、上記の第１段目の乳化重合反応液に、予備乳化液を添加して行う重合である。
上記予備乳化液とは、重合性紫外線安定性単量体及び／又は重合性光安定性単量体を予備乳化した乳化液であり、好ましくは、上記重合性紫外線安定性単量体及び／又は重合性光安定性単量体と、（メタ）アクリル酸系単量体とを予備乳化した乳化液である。この（メタ）アクリル酸系単量体とは、上記した（メタ）アクリル酸系単量体を用いることができる。
【００２１】
上記第２段目の乳化重合において、予備乳化液に（メタ）アクリル酸系単量体を加える場合、この（メタ）アクリル酸系単量体の使用量は、乳化重合に用いられる（メタ）アクリル酸系単量体全量の０〜３０重量％、好ましくは５〜２０重量％とするのがよい。３０重量％より多いと、全体の重合系のバランスが悪くなる場合がある。また、（メタ）アクリル酸系単量体は０重量％でもよいが、５重量％未満の場合は、上記重合性紫外線安定性単量体及び／又は重合性光安定性単量体の反応が不十分となる場合があり、未反応のままこれらが残留する場合がある。
【００２２】
なお、後述する第１段目の重合の転化率は、この第２段目の重合に用いられる（メタ）アクリル酸系単量体を除いた、第１段目の乳化重合に供した単量体についての値を示す。
【００２３】
上記第２段目の乳化重合において、上記重合性紫外線安定性単量体及び／又は重合性光安定性単量体に併せて、（メタ）アクリル酸系単量体を用いることにより、上記各単量体の重合体への取り込みが容易となり、反応効率が向上する。
【００２４】
上記重合性紫外線安定性単量体又は重合性光安定性単量体とは、重合性を有する紫外線安定剤又は光安定剤をいい、ヒンダードアミンライトスタビライザー（以下、「ＨＡＬＳ」と略する。）基を有するアクリレート（以下、「重合性ＨＡＬＳ」と称する。）やフェノール系酸化防止剤基を有するアクリレート等を例としてあげることができる。この重合性ＨＡＬＳの具体例としては、メタクリル酸１，２，２，６，６−ペンタメチルピペリジニル（旭電化工業（株）製；ＬＡ−８２、日立化成工業（株）製；ＪＡ−７１１ＭＭ）、アクリル酸２，２，６，６−テトラメチルピペリジニル（旭電化工業（株）製；ＬＡ−８７、日立化成工業（株）製；ＪＡ−７１２ＭＭ）等があげられる。
【００２５】
上記の（メタ）アクリル酸系単量体と、重合性紫外線安定性単量体及び／又は重合性光安定性単量体とを予備乳化して乳化液とする場合、乳化剤を用いるのが好ましい。この乳化剤の例としては、上記した乳化剤があげられる。
この重合性紫外線安定性単量体及び／又は重合性光安定性単量体の使用量は、得られる塗料用エマルジョン組成物の固形分１００重量部に対して、０．０１〜５重量部がよく、０．１〜３重量部が好ましい。０．０１重量部より少ないと、目的とする耐候性改良効果が不十分となることがある。一方、５重量部より多いと、添加量の増量に見合う耐候性改良効果が得られず、経済的でなく、また、エマルジョンの安定性を阻害したり、重合体の分子量低下を起こすことがある。
【００２６】
上記予備乳化液には、必要に応じて、重合開始剤を含有させることができる。これは、一般に、上記重合性紫外線安定性単量体や重合性光安定性単量体は、ラジカル重合反応中に生じるラジカルのトラップ剤としての機作を有するために重合抑制作用を有する。このため、これらを重合反応に供与することにより、反応が停止する場合があり、これを防ぐため重合開始剤を含有させるのが好ましい。
【００２７】
上記重合開始剤の予備乳化液への添加量は、０．０１〜５重量％が好ましく、０．０５〜２重量％がより好ましい。０．０１重量％より少ないと、未反応単量体の残存量が多くなる。一方、５重量％より多いと、重合体の分子量が低くなり、あるいは、未分解の重合開始剤が残留して、耐候性が悪化する。
【００２８】
上記予備乳化液の添加方法は、一括に添加してもよく、また、一定時間かけて、連続的又は断続的に添加してもよい。
なお、上記予備乳化液を調製する際には、撹拌・混合による方法や、ホモジナイザー等の機械的剪断力を加える方法を適宜用いることができる。
【００２９】
この第２段の乳化重合における反応温度は、特に限定されないが、第１段における反応温度と同様若しくは少し温度を上げて重合させるのが好ましい。
【００３０】
上記予備乳化液の上記の第１段の乳化重合液への添加開始時期は、第１段の乳化重合における、単量体の転化率が７０％以上に達した後であり、７５〜９９．９％に達した後が好ましい。
【００３１】
なお、この単量体の転化率は、別途行うモデル実験により、後述の方法で転化率を測定して、反応時間と転化率との関係を予め求めておき、実際の乳化重合反応で、この反応時間と転化率との関係を適用して、転化率を判定してもよい。また、適時サンプルを採取して、下記の方法で直接転化率を測定してもよい。
【００３２】
第１段の乳化重合における単量体の転化率が上記の範囲を満たす場合は、第１段の乳化重合反応の重合反応速度が高い状態にあり、一般的には、この状態は、外部から冷却して反応温度を所定の範囲内に保とうとする状態の場合である。このときに、上記予備乳化液を添加すると、この予備乳化液に含まれる重合性紫外線安定性単量体及び／又は重合性光安定性単量体も同時に添加されることとなる。この重合性紫外線安定性単量体及び／又は重合性光安定性単量体は、上記の通り重合抑制作用を有するが、第１段の乳化重合反応の重合反応速度が高い状態であるため、この重合性紫外線安定性単量体及び／又は重合性光安定性単量体の添加によって重合が抑制され、重合反応速度が低くなるまでに、第２段目の重合のほとんどが進行し、また、重合性紫外線安定性単量体及び／又は重合性光安定性単量体も容易に重合される。このため、重合性紫外線安定性単量体及び／又は重合性光安定性単量体を重合体中に取り込んだ、十分な平均分子量を有するエマルジョン組成物を得ることができる。
【００３３】
この発明にかかる製造方法で得られるエマルジョン組成物は、塗料用として使用することができ、これから得られる塗膜は、十分な耐候性や光沢性を有する。また、帯電しにくいため、耐汚染性にも優れている。
【００３４】
【実施例】
以下、本発明を実施例を用いてより詳細に説明する。まず、実施例及び比較例で行った試験及び評価方法、及び使用した各成分について説明する。
【００３５】
＜試験及び評価方法＞
［重合率の測定（不揮発分測定−簡易法−）］
アルミカップに重合過程の樹脂エマルジョン１ｇを測りとり、電子レンジで１０分間処理して水分及び未反応単量体を揮散させた後に秤量し、重合率を算出した。
【００３６】
［重合性の評価］
得られたエマルジョンの臭気の官能試験により、重合の進行状態を評価した。
○：臭気なし
△：臭気が僅かにあり
×：臭気が著しい
【００３７】
［ガラス転移温度（Ｔｇ）の測定］
示差走査熱量分析（ＤＳＣ）（セイコー電子工業（株）製 示差走査熱量計ＤＳＣ−２２０Ｃ型）法によって測定した。
【００３８】
［不揮発分の測定］
重合終了後の樹脂エマルジョンを、ＪＩＳ Ｋ ６８３３に記載の規定に従って測定した。
【００３９】
［粘度の測定］
重合終了後の樹脂エマルジョンを、ＪＩＳ Ｋ ６８３３に記載の規定に準じて、ＢＭ型粘度計を用いて、２５℃、１２ｒｐｍ、＃２ロータにて測定した。
【００４０】
［ｐＨの測定］
重合終了後の樹脂エマルジョンを、ＪＩＳ Ｋ ６８３３に記載の規定に従って測定した。
【００４１】
［塗料安定性の判定］
ＪＩＳ Ｋ ５４００に記載の規定に準じて、密閉容器に実施例又は比較例で得られた塗料を採取し、３５℃恒温槽に９０日間放置して粘度上昇及び凝集物の有無を目視判定した。
【００４２】
［初期光沢の測定］
溶剤系塩化ゴムシーラーをケイカル板（ＪＩＳ Ａ ５４３０規定のもの、日本テストパネル（株）製）に、１００ｇ／ｍ2刷毛塗りした後、常温で２時間経過後、実施例又は比較例で得られた塗料をエアスプレーにて１００ｇ／ｍ2の塗装量となるように塗装し、２０℃、６５％ＲＨで７日間養生して、試験片を調製した。
得られた試験片を、ＪＩＳ Ｋ ５４００に記載の規定に準じて、デジタルグロスメーター（日本電色工業（株）製：ＵＶＧ−５０）を用いて、６０°鏡面初期光沢（Ｇ0）を測定した。
【００４３】
［光沢保持率の測定］
上記の試験片を、スーパーＵＶ試験機（岩崎電気（株）製：ＳＵＶ１５１型）を用いて、紫外線照射８時間／結露４時間の条件下で所定時間処理した後、上記デジタルグロスメーターを用いて、６０°鏡面光沢（Ｇn）を測定し、次の式から光沢保持率を算出した。
光沢保持率（％）＝（Ｇn／Ｇ0）×１００
【００４４】
［耐汚染性（色差）及び耐候性の測定］
ＪＩＳ Ｋ ８７２２に記載の規定に準じて、上記の方法で製造した試験片の塗膜の色彩（Ｌ0，ａ0，ｂ0）を、色彩色差計（ミノルタカメラ（株）製：ＣＲ−３００型）を用いて測定した。
次に、屋外曝露台に試験片を設置し、３ヶ月間曝露した後、上記色彩色差計を用いて、色彩（Ｌ，ａ，ｂ）を測定し、次の式から色差（ΔＥ*ab）及び曝露試験前後のＬ値の差（ΔＬ＝Ｌ−Ｌ0）を算出した。このΔＬが小さいほど、耐汚染性が高いことを意味する。また、ΔＥ*abが小さいほど、耐候性が良いと評価する。
ΔＥ*ab＝｛（Ｌ−Ｌ0）2＋（ａ−ａ0）2＋（ｂ−ｂ0）2｝1/2
【００４５】
＜原材料＞
・メタクリル酸メチル…三菱レイヨン（株）製（以下、「ＭＭＡ」と略する。）
・メタクリル酸シクロヘキシル…旭化成（株）製（以下、「ＣＨＭＡ」と略する。）
・アクリル酸ブチル…三菱化学（株）製（以下、「ＢＡ」と略する。）
・アクリル酸メチル…三菱化学（株）製（以下、「ＭＡ」と略する。）
・メタクリル酸１，２，２，６，６−ペンタメチルピペリジニル（旭電化工業（株）製；ＬＡ−８２）（以下、「ＬＡ８２」と略する。）
・アクリル酸２，２，６，６−テトラメチルピペリジニル（旭電化工業（株）製；ＬＡ−８７）（以下、「ＬＡ８７」と略する。）
【００４６】
（実施例１〜４、比較例１〜２）
撹拌機、温度調節機、温度計、還流冷却器、滴下ロート及び窒素ガス導入管を備えた反応容器内に、ポリオキシエチレンアルキルフェニルエーテル硫酸アンモニウム（９８％水溶液）０．３重量部、及び脱イオン水５０重量部を仕込み、６５℃に昇温しながら窒素ガスを導入した。そして過硫酸アンモニウム０．３重量部を添加した。次に、表１に記載の各単量体を表１に記載の重量部、及びポリオキシアルキルフェニルエーテル４重量部を脱イオン水５０重量部に分散させ、これを３時間かけて滴下した。このときの反応温度を６５℃に保持した。
【００４７】
上記重合反応液中の単量体の転化率が８５％となったところで、７５℃に昇温し、表１に記載の重合性ＨＡＬＳを表１に記載の重量部とＢＡ２重量部を脱イオン水２重量部に分散させた予備乳化液を添加し、続いて、ＡＤＶＮ（２,２−アゾビス（２，４−ジメチルバレロニトリル））０．１重量部を添加し、３．５時間熟成した。その後、冷却し、２５％アンモニア水を１．５重量部添加して中和して樹脂エマルジョンを得た。
【００４８】
この得られた樹脂エマルジョン１００重量部に酸化チタン含量６９重量％のチタンペースト３０重量部及びジエチレングリコールモノブチルエーテルアセテートを添加して、最低造膜温度を０℃に調整した塗料を得た。
得られた樹脂エマルジョン及び塗料を用いて、上記の測定及び評価を行った。その結果を表１に示す。
【００４９】
【表１】
【発明の効果】
この発明にかかる塗料用エマルジョン組成物は、塗膜にしたとき、十分な耐候性及び光沢性、光沢保持性を有し、さらに、耐汚染性にも優れる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an emulsion composition for paint.
[0002]
[Prior art]
Conventionally, a water-based (meth) acrylic resin emulsion-type paint has been used as a paint for coating interior and exterior wall materials of buildings. Because this paint is a water-based paint, it can be applied directly to wet surfaces when compared with solvent-based paints, is easy to handle, does not generate solvent odor, and may cause fire or explosion. This is because it has the characteristics of being less expensive and relatively inexpensive.
[0003]
However, the coating film formed from this water-based (meth) acrylic resin emulsion-type paint has a problem that the weather resistance is insufficient and the gloss is inferior to that of the solvent-type paint.
[0004]
On the other hand, JP-A-3-128978 and JP-A-5-140240 disclose resin compositions for coatings which are radically polymerized using a cycloalkyl group-containing monomer, a polymerizable UV-stable monomer or the like as a raw material monomer. Yes. Japanese Patent Application Laid-Open No. 7-133458 discloses a resin composition for coating that is radically polymerized using isobornyl (meth) acrylate, a light stability-imparting monomer or the like as a raw material monomer.
These resin compositions for paints are characterized by excellent weather resistance and gloss.
[0005]
[Problems to be solved by the invention]
However, since the above-mentioned polymerizable UV-stable monomer and light-stabilizing monomer have the property of trapping radicals, the above-mentioned radical polymerization exhibits an effect of suppressing the polymerization reaction. For this reason, a large amount of polymerization initiator is required, chain transfer to the polymerization initiator becomes remarkable, and the average molecular weight of the resulting resin cannot be increased so much, and the weather resistance and glossiness of the resulting resin composition for paints are However, it may not always be sufficient.
[0006]
Then, this invention aims at providing the manufacturing method of the resin composition for water-based paints excellent in sufficient weather resistance and glossiness.
[0007]
[Means for Solving the Problems]
In the present invention, a (meth) acrylic acid-based monomer is subjected to first-stage emulsion polymerization in an aqueous medium, and after the conversion rate reaches 70% or more, the polymerizable UV-stable monomer and / or polymerization is performed. A pre-emulsified solution preliminarily emulsified with a light-stable monomer, preferably a pre-emulsified solution preliminarily emulsified with a (meth) acrylic acid monomer, to carry out the second stage emulsion polymerization Thus, the above problem has been solved.
[0008]
The emulsion polymerization reaction is divided into two stages. First, the first stage of emulsion polymerization is carried out, and when the polymerization reaction rate at this stage is high, the polymerizable UV-stable monomer and / or the polymerizable light-stable monomer. A pre-emulsion containing the monomer is added to perform the second stage emulsion polymerization. For this reason, even if the polymerization reaction is suppressed by the polymerizable UV-stable monomer and / or polymerizable light-stable monomer, most of the second-stage polymerization is not performed until the polymerization reaction rate decreases. In addition, the polymerizable UV-stable monomer and / or the polymerizable light-stable monomer are also easily polymerized and incorporated into the polymer.
In addition, by using a (meth) acrylic acid-based monomer in the second stage of emulsion polymerization, a polymer of the above-described polymerizable UV-stable monomer and / or polymerizable light-stable monomer is used. Incorporation into the inside becomes easy and the reaction efficiency is further improved.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
The method for producing a coating emulsion composition according to the present invention is a method for carrying out two-stage emulsion polymerization.
[0010]
The first stage emulsion polymerization is carried out by polymerizing a (meth) acrylic acid monomer in an aqueous medium. As this (meth) acrylic acid monomer, (meth) acrylic acid alkyl ester, (meth) acrylic monomer having a cycloalkyl group, (meth) acrylic monomer, (meth) acrylic Examples thereof include acid alkoxyalkyl esters and cross-linkable (meth) acrylic acid alkyl esters. In the polymerization, one kind or two or more kinds may be used.
[0011]
Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) Benzyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.
[0012]
Examples of the (meth) acrylic acid monomer having a cycloalkyl group include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.
Examples of the (meth) acrylic acid monomer include acrylic acid and methacrylic acid.
[0013]
Examples of the alkoxyalkyl ester of (meth) acrylic acid include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and the like.
[0014]
Examples of the cross-linkable (meth) acrylic acid alkyl ester include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. .
In this specification, “(meth) acryl” means “acryl or methacryl”.
[0015]
The first stage emulsion polymerization method is not particularly limited, and is suitably performed from various emulsion polymerization methods such as a batch polymerization method, a monomer dropping polymerization method, and an emulsion monomer dropping polymerization method performed in a normal aqueous medium. Can be selected and adopted. Among these, the monomer dropping polymerization method and the emulsion monomer dropping polymerization method are particularly preferable in securing the stability of the emulsion during production.
[0016]
Examples of the aqueous medium include water and a water-water-soluble solvent mixture obtained by mixing water and a water-soluble solvent such as methanol, ethanol, and propanol. Among these, water is particularly preferable.
[0017]
As the polymerization initiator used in the first stage emulsion polymerization, a polymerization initiator used in usual emulsion polymerization can be used. Examples of the polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero). Nitrile) and other azo compounds, hydrogen peroxide, hydroperoxides such as t-butyl hydroperoxide, radical polymerization initiators such as peroxides such as benzoyl peroxide and lauroyl peroxide, and these are independent. Or 2 or more types can be mixed and used. These radical polymerization initiators can be used as a redox polymerization initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, sodium thiosulfate, tartaric acid, L-ascorbic acid.
[0018]
In this emulsion polymerization, an emulsifier can be used in order to improve the stability of the emulsion. The emulsifier is not particularly limited as long as it is usually used for emulsion polymerization, and examples thereof include anionic, cationic and amphoteric ionic surfactants and nonionic surfactants.
[0019]
The reaction solution at the time of emulsion polymerization can be adjusted in pH by using a pH adjusting agent such as aqueous ammonia at the time of emulsion polymerization from the viewpoint of the stability of the polymerization. Moreover, it is preferable that reaction temperature is about 50-100 degreeC normally and reaction time is about 2-16 hours normally.
[0020]
Next, the second stage emulsion polymerization is a polymerization performed by adding a preliminary emulsion to the first stage emulsion polymerization reaction liquid.
The preliminary emulsion is an emulsion obtained by pre-emulsifying a polymerizable UV-stable monomer and / or a polymerizable light-stable monomer, preferably the polymerizable UV-stable monomer and / or It is an emulsion obtained by pre-emulsifying a polymerizable light-stable monomer and a (meth) acrylic acid monomer. As the (meth) acrylic acid monomer, the above-mentioned (meth) acrylic acid monomer can be used.
[0021]
In the second stage emulsion polymerization, when a (meth) acrylic acid monomer is added to the preliminary emulsion, the amount of the (meth) acrylic monomer used is the emulsion polymerization (meth). It is good to set it as 0-30 weight% of the total amount of acrylic acid monomers, Preferably it is 5-20 weight%. If it exceeds 30% by weight, the balance of the whole polymerization system may be deteriorated. In addition, the (meth) acrylic acid monomer may be 0% by weight, but in the case of less than 5% by weight, the reaction of the polymerizable UV-stable monomer and / or the polymerizable light-stable monomer is carried out. It may become insufficient, and these may remain unreacted.
[0022]
The conversion rate of the first-stage polymerization described later is a single amount subjected to the first-stage emulsion polymerization excluding the (meth) acrylic acid monomer used for the second-stage polymerization. Indicates the value for the body.
[0023]
In the second stage emulsion polymerization, by using a (meth) acrylic acid monomer in combination with the polymerizable UV stable monomer and / or polymerizable light stable monomer, Incorporation of the monomer into the polymer is facilitated, and the reaction efficiency is improved.
[0024]
The polymerizable UV-stable monomer or polymerizable light-stable monomer refers to a polymerizable UV-stabilizer or light-stabilizer, and is a hindered amine light stabilizer (hereinafter abbreviated as “HALS”) group. Examples thereof include acrylates having an acrylate (hereinafter referred to as “polymerizable HALS”), acrylates having a phenolic antioxidant group, and the like. Specific examples of this polymerizable HALS include 1,2,2,6,6-pentamethylpiperidinyl methacrylate (manufactured by Asahi Denka Kogyo Co., Ltd .; LA-82, manufactured by Hitachi Chemical Co., Ltd .; JA- 711MM), 2,2,6,6-tetramethylpiperidinyl acrylate (manufactured by Asahi Denka Kogyo Co., Ltd .; LA-87, manufactured by Hitachi Chemical Co., Ltd .; JA-712MM), and the like.
[0025]
When pre-emulsifying the (meth) acrylic acid monomer and the polymerizable UV-stable monomer and / or polymerizable light-stable monomer into an emulsion, it is preferable to use an emulsifier. . Examples of this emulsifier include the above-mentioned emulsifiers.
The amount of the polymerizable UV-stable monomer and / or polymerizable light-stable monomer used is 0.01 to 5 parts by weight with respect to 100 parts by weight of the solid content of the resulting coating emulsion composition. It is preferably 0.1 to 3 parts by weight. If it is less than 0.01 parts by weight, the intended effect of improving weatherability may be insufficient. On the other hand, if the amount is more than 5 parts by weight, the effect of improving the weather resistance commensurate with the increase in the amount added cannot be obtained, and it is not economical, and the stability of the emulsion may be hindered or the molecular weight of the polymer may be lowered. .
[0026]
The preliminary emulsified liquid may contain a polymerization initiator as necessary. In general, the polymerizable UV-stable monomer and the polymerizable light-stable monomer have a function as a trapping agent for radicals generated during the radical polymerization reaction, and thus have a polymerization inhibitory action. For this reason, by donating these to the polymerization reaction, the reaction may be stopped. In order to prevent this, it is preferable to contain a polymerization initiator.
[0027]
The amount of the polymerization initiator added to the preliminary emulsion is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight. If it is less than 0.01% by weight, the residual amount of unreacted monomer increases. On the other hand, when the content is more than 5% by weight, the molecular weight of the polymer becomes low, or an undecomposed polymerization initiator remains and the weather resistance deteriorates.
[0028]
The method for adding the preliminary emulsion may be added all at once, or may be added continuously or intermittently over a certain period of time.
In addition, when preparing the said preliminary | backup emulsion, the method of applying mechanical shearing force, such as the method by stirring and mixing, and a homogenizer, can be used suitably.
[0029]
The reaction temperature in the second stage emulsion polymerization is not particularly limited, but it is preferable to perform polymerization at the same temperature as or slightly higher than the reaction temperature in the first stage.
[0030]
The start of addition of the preliminary emulsion to the first-stage emulsion polymerization liquid is after the monomer conversion in the first-stage emulsion polymerization has reached 70% or more. After reaching 9% is preferred.
[0031]
Incidentally, the conversion rate of this monomer was determined by measuring the conversion rate by a method to be described later in a model experiment performed separately, and obtaining the relationship between the reaction time and the conversion rate in advance. The conversion rate may be determined by applying the relationship between the reaction time and the conversion rate. Alternatively, a sample may be taken in a timely manner and the conversion rate may be measured directly by the following method.
[0032]
When the conversion rate of the monomer in the first stage emulsion polymerization satisfies the above range, the polymerization reaction rate of the first stage emulsion polymerization reaction is in a high state. This is the case where the reaction temperature is to be kept within a predetermined range by cooling. At this time, when the preliminary emulsion is added, the polymerizable UV-stable monomer and / or polymerizable light-stable monomer contained in the preliminary emulsion is also added at the same time. This polymerizable UV-stable monomer and / or polymerizable light-stable monomer has a polymerization inhibitory action as described above, but because the polymerization reaction rate of the first stage emulsion polymerization reaction is high, By the addition of this polymerizable UV-stable monomer and / or polymerizable light-stable monomer, the polymerization is suppressed, and most of the second stage polymerization proceeds until the polymerization reaction rate decreases, and Polymerizable UV-stable monomers and / or polymerizable light-stable monomers are also easily polymerized. Therefore, it is possible to obtain an emulsion composition having a sufficient average molecular weight in which a polymerizable UV-stable monomer and / or polymerizable light-stable monomer is incorporated into the polymer.
[0033]
The emulsion composition obtained by the production method according to the present invention can be used for coatings, and the coating film obtained therefrom has sufficient weather resistance and gloss. Further, since it is difficult to be charged, it is excellent in stain resistance.
[0034]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. First, tests and evaluation methods conducted in Examples and Comparative Examples and each component used will be described.
[0035]
<Test and evaluation method>
[Measurement of polymerization rate (nonvolatile content measurement-simple method)]
1 g of the resin emulsion in the polymerization process was measured in an aluminum cup, treated for 10 minutes in a microwave oven to volatilize moisture and unreacted monomers, and weighed to calculate the polymerization rate.
[0036]
[Evaluation of polymerizability]
The progress of polymerization was evaluated by a sensory test of the odor of the obtained emulsion.
○: No odor △: There is a slight odor ×: The odor is remarkable [0037]
[Measurement of glass transition temperature (Tg)]
Differential scanning calorimetry (DSC) (Seiko Denshi Kogyo Co., Ltd. differential scanning calorimeter DSC-220C type) was used for measurement.
[0038]
[Measurement of non-volatile content]
The resin emulsion after the polymerization was measured according to the rules described in JIS K 6833.
[0039]
[Measurement of viscosity]
The resin emulsion after the completion of polymerization was measured with a # 2 rotor at 25 ° C., 12 rpm using a BM type viscometer in accordance with the rules described in JIS K 6833.
[0040]
[Measurement of pH]
The resin emulsion after the polymerization was measured according to the rules described in JIS K 6833.
[0041]
[Judgment of paint stability]
In accordance with the provisions described in JIS K 5400, the paints obtained in Examples or Comparative Examples were collected in a sealed container and left in a thermostatic bath at 35 ° C. for 90 days to visually determine the increase in viscosity and the presence of aggregates.
[0042]
[Measurement of initial gloss]
After applying solvent-based chlorinated rubber sealer to a calcare board (JIS A 5430 regulation, manufactured by Nippon Test Panel Co., Ltd.) with a brush of 100 g / m 2 , it is obtained in Example or Comparative Example after 2 hours at room temperature. The paint was applied by air spray so that the coating amount was 100 g / m 2 and cured at 20 ° C. and 65% RH for 7 days to prepare a test piece.
The obtained specimen is measured for 60 ° specular initial gloss (G 0 ) using a digital gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd .: UVG-50) in accordance with the provisions described in JIS K 5400. did.
[0043]
[Gloss retention measurement]
The test piece was treated for a predetermined time under the conditions of ultraviolet irradiation 8 hours / condensation 4 hours using a super UV tester (Iwasaki Electric Co., Ltd. product: SUV151 type), and then using the digital gloss meter. The 60 ° specular gloss (G n ) was measured, and the gloss retention was calculated from the following formula.
Gloss retention rate (%) = (G n / G 0 ) × 100
[0044]
[Measurement of stain resistance (color difference) and weather resistance]
In accordance with the provisions described in JIS K 8722, the color (L 0 , a 0 , b 0 ) of the coating film of the test piece produced by the above method was converted into a color difference meter (Minolta Camera Co., Ltd .: CR-300). Type).
Next, after placing the test piece on the outdoor exposure table and exposing for 3 months, the color (L, a, b) is measured using the above color difference meter, and the color difference (ΔE * ab ) is calculated from the following equation. And the difference (ΔL = L−L 0 ) between the L values before and after the exposure test was calculated. A smaller ΔL means higher contamination resistance. Moreover, it is evaluated that the weather resistance is better as ΔE * ab is smaller.
ΔE * ab = {(L−L 0 ) 2 + (a−a 0 ) 2 + (b−b 0 ) 2 } 1/2
[0045]
<Raw materials>
・ Methyl methacrylate: Mitsubishi Rayon Co., Ltd. (hereinafter abbreviated as “MMA”)
・ Cyclohexyl methacrylate: manufactured by Asahi Kasei Corporation (hereinafter abbreviated as “CHMA”).
・ Butyl acrylate: manufactured by Mitsubishi Chemical Corporation (hereinafter abbreviated as “BA”)
・ Methyl acrylate: manufactured by Mitsubishi Chemical Corporation (hereinafter abbreviated as “MA”)
-1,2,2,6,6-pentamethylpiperidinyl methacrylate (Asahi Denka Kogyo Co., Ltd .; LA-82) (hereinafter abbreviated as “LA82”)
Acrylic acid 2,2,6,6-tetramethylpiperidinyl (Asahi Denka Kogyo Co., Ltd .; LA-87) (hereinafter abbreviated as “LA87”)
[0046]
(Examples 1-4, Comparative Examples 1-2)
In a reaction vessel equipped with a stirrer, temperature controller, thermometer, reflux condenser, dropping funnel and nitrogen gas introduction tube, 0.3 part by weight of polyoxyethylene alkylphenyl ether ammonium sulfate (98% aqueous solution) and deionized 50 parts by weight of water was charged, and nitrogen gas was introduced while raising the temperature to 65 ° C. And 0.3 weight part of ammonium persulfate was added. Next, each of the monomers listed in Table 1 was dispersed in 50 parts by weight of deionized water and 4 parts by weight of polyoxyalkyl phenyl ether dispersed in 3 parts by weight over 3 hours. The reaction temperature at this time was kept at 65 ° C.
[0047]
When the conversion rate of the monomer in the polymerization reaction solution reached 85%, the temperature was raised to 75 ° C., and the polymerizable HALS shown in Table 1 was deionized into the parts by weight shown in Table 1 and 2 parts by weight of BA. A preliminary emulsion dispersed in 2 parts by weight of water was added, and then 0.1 part by weight of ADVN (2,2-azobis (2,4-dimethylvaleronitrile)) was added, followed by aging for 3.5 hours. . Thereafter, the mixture was cooled and neutralized by adding 1.5 parts by weight of 25% aqueous ammonia to obtain a resin emulsion.
[0048]
To 100 parts by weight of the obtained resin emulsion, 30 parts by weight of titanium paste having a titanium oxide content of 69% by weight and diethylene glycol monobutyl ether acetate were added to obtain a paint whose minimum film forming temperature was adjusted to 0 ° C.
Said measurement and evaluation were performed using the obtained resin emulsion and coating material. The results are shown in Table 1.
[0049]
[Table 1]
【The invention's effect】
The coating emulsion composition according to the present invention has sufficient weather resistance, glossiness and gloss retention when formed into a coating film, and is excellent in stain resistance.
Claims (3)
上記予備乳化液が、重合性紫外線安定性単量体及び／又は重合性光安定性単量体と、（メタ）アクリル酸系単量体とを予備乳化したものであり、上記予備乳化液中に含まれる（メタ）アクリル酸系単量体の含有量は、乳化重合に用いられる（メタ）アクリル酸系単量体全量の０重量％を超えて３０重量％以下である、塗料用エマルジョン組成物の製造方法。The first stage emulsion polymerization of the (meth) acrylic acid monomer in an aqueous medium is carried out, and after the conversion rate reaches 75 to 99.9%, the polymerizable UV-stable monomer and / or polymerizability is reached. the preliminary emulsion was pre-emulsified photostability monomer, or added on which contains the polymerization initiator, or the emulsion polymerization of the second stage by adding a polymerization initiator after addition of the pre-emulsion Done
The pre-emulsified liquid is a pre-emulsified polymerizable UV-stable monomer and / or polymerizable light-stable monomer and a (meth) acrylic acid monomer, the content of free (meth) acrylic acid monomer, the emulsion polymerization is 30 wt% or less than 0 wt% of are (meth) acrylic acid monomer based on the total amount used, paint emulsion composition Manufacturing method.
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