JPH02251502A - Preparation of crosslinking agent-containing emulsified polymer emulsion - Google Patents
Preparation of crosslinking agent-containing emulsified polymer emulsionInfo
- Publication number
- JPH02251502A JPH02251502A JP7042889A JP7042889A JPH02251502A JP H02251502 A JPH02251502 A JP H02251502A JP 7042889 A JP7042889 A JP 7042889A JP 7042889 A JP7042889 A JP 7042889A JP H02251502 A JPH02251502 A JP H02251502A
- Authority
- JP
- Japan
- Prior art keywords
- component
- emulsion
- water
- crosslinking agent
- group
- 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.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 27
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 title abstract description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 239000004908 Emulsion polymer Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- -1 vinylcyclohexenyl Chemical group 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen 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
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AVWQQPYHYQKEIZ-UHFFFAOYSA-K trisodium;2-dodecylbenzenesulfonate;3-dodecylbenzenesulfonate;4-dodecylbenzenesulfonate Chemical compound [Na+].[Na+].[Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCCCCCCCC1=CC=CC(S([O-])(=O)=O)=C1.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O AVWQQPYHYQKEIZ-UHFFFAOYSA-K 0.000 description 1
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- 229960003986 tuaminoheptane Drugs 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、非水溶性架橋剤を乳化重合体粒子中に内包さ
せてなる重合体エマルジョンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer emulsion in which a water-insoluble crosslinking agent is encapsulated in emulsion polymer particles.
乳化重合体粒子中に架橋剤を内包したエマルジョンはす
でに知られている。しかし、架橋硬化性の観点から、該
粒子内に多量の架橋剤を含有せしめると、乳化重合中に
凝集物が発生したり、乳化重合体の安定性が低下したり
する問題を生じる。Emulsions in which crosslinking agents are encapsulated in emulsion polymer particles are already known. However, from the viewpoint of crosslinking and curability, if a large amount of crosslinking agent is contained in the particles, problems such as generation of aggregates during emulsion polymerization and a decrease in the stability of the emulsion polymer arise.
これを改良するためには界面活性剤の使用量を架橋剤の
無い場合より増やすしかないが、そうすると加熱硬化塗
膜の耐水性、耐食性、上塗との眉間付着性などが低下す
る等の問題がある。このため、架橋剤内包乳化重合体エ
マルジョンは、高度な性能を要求される加熱硬化型塗料
として充分実用化されるに至っていないのが現状である
。In order to improve this, the only way to improve this is to increase the amount of surfactant used compared to when no crosslinking agent is used, but this causes problems such as a decrease in the water resistance, corrosion resistance, and glabellar adhesion of the heat-cured coating film. be. For this reason, at present, crosslinking agent-containing emulsion polymer emulsions have not yet been fully put to practical use as heat-curable coatings that require high performance.
本発明は上記問題点を解決し、架橋剤を多量内包しても
凝集物が発生することがなく、常温で安定で、かつ塗装
後加熱により高性能の硬化塗膜を形成しうる架橋剤含有
乳化重合体二１ルジョンの製造方法に関する。即ち、本
発明は（Ａ）アリル基含有界面活性剤［以下、（Ａ）成
分という］及び（Ｂ）非水溶性架橋剤Ｅ以下、（Ｂ）成
分という１の存在下で（Ｃ）エチレン性不飽和七ツマー
Ｅ以下、（Ｃ）成分という］を乳化重合させることを特
徴とする架橋剤含有乳化重合体エマルジョンの製造方法
を提供するものである。The present invention solves the above problems, and contains a cross-linking agent that does not generate aggregates even when a large amount of cross-linking agent is included, is stable at room temperature, and can form a high-performance cured coating film by heating after painting. The present invention relates to a method for producing emulsion polymer 21ulsion. That is, the present invention provides (C) an ethylenic compound in the presence of (A) an allyl group-containing surfactant [hereinafter referred to as component (A)] and (B) a water-insoluble crosslinking agent E hereinafter referred to as component (B). The present invention provides a method for producing a crosslinking agent-containing emulsion polymer emulsion, which comprises emulsion polymerizing an unsaturated heptamer E (hereinafter referred to as component (C)).
本発明の１つの特徴は、乳化重合用界面活性剤としてア
リル基含有界面活性剤［（Ａ）成分Ｊを用いたところに
ある。該（Ａ）成分のアリル基（ＣＨ！−ＣＨ−ＣＨ，
−）は乳化重合反応において、単独で重合することは殆
んどなく、他の重合性不飽和上ツマ−［例えば、上記（
Ｃ）成分］と共重合する性質がある。したがって、上記
（Ａ）および（Ｂ）成分の存在下で（Ｃ）成分を乳化重
合すると、（Ｂ）成分は非水溶性であるために水中で微
粒子状に分散し、その周囲において（Ｃ）成分の乳化重
合が行なわれて、（Ｂ）成分を内包する（Ｃ）成分の微
粒子状乳化重合体が形成され、一方、（Ａ）成分につい
てみると、アリール基は（Ｃ）成分の乳化重合時に該（
Ｃ）成分の一部と共重合して乳化重合体微粒子の表層に
化学的に結合し、（Ａ）成分の親水基部分は水中に浮遊
しているものと思われる。その結果、該（Ａ）成分は、
それ単独で重合体粒子を形成することが殆んどなく、少
なくともその大部分は（Ｃ）成分の一部と共重合し、（
Ｂ）成分と（Ｃ）成分とからなる乳化重合体微粒子と化
学的に結合しているために、該微粒子を水中に安定して
分散させるという界面活性剤の機能を効率的に発揮では
、内包させる（Ｂ）成分が多量であっても生成するエマ
ルジョンは安定であり、凝集物を発生することは殆んど
なくなる。しかも、本発明のエマルジョンには架橋剤の
単独微粒子や（Ａ）と（Ｂ）成分とからなる微粒子も殆
ど存在しないと思われる。勿論、アリル基不合界面活性
剤を上記本発明の特徴を失なわない範囲で併用してもか
まわない。One feature of the present invention is that an allyl group-containing surfactant [(A) component J] is used as a surfactant for emulsion polymerization. The allyl group (CH!-CH-CH,
-) rarely polymerizes alone in emulsion polymerization reactions, and other polymerizable unsaturated polymers [for example, (
It has the property of copolymerizing with component C). Therefore, when component (C) is emulsion polymerized in the presence of components (A) and (B) above, component (B) is water-insoluble, so it is dispersed in the form of fine particles in water, and around it, (C) The emulsion polymerization of the components is carried out to form a fine particulate emulsion polymer of the component (C) which includes the component (B).On the other hand, regarding the component (A), the aryl group is formed in the emulsion polymerization of the component (C). Sometimes applicable (
It is thought that it is copolymerized with a part of component C) and chemically bonded to the surface layer of the emulsion polymer fine particles, and the hydrophilic group portion of component (A) is suspended in the water. As a result, the component (A) is
It hardly forms polymer particles by itself, and at least most of it copolymerizes with a part of component (C).
Because it is chemically bonded to the emulsion polymer fine particles consisting of component B) and component (C), it effectively performs the surfactant's function of stably dispersing the fine particles in water. Even if a large amount of component (B) is used, the resulting emulsion is stable and almost no aggregates are formed. Furthermore, it seems that there are almost no individual fine particles of the crosslinking agent or fine particles composed of components (A) and (B) in the emulsion of the present invention. Of course, an allyl group-unbonded surfactant may be used in combination as long as the characteristics of the present invention described above are not lost.
以下、本発明の方法についてさらに詳細に説明する。The method of the present invention will be explained in more detail below.
（Ａ）成分ニアリール基含有界面活性剤１分子中に１個
のアリル基と、親木基及び疎水基とを有するものであれ
ば、アニオン性、カチオン性、両性及びノニオン性のい
ずれのタイプの界面活性剤でも使用することができる。(A) Component naryl group-containing surfactant Any type of surfactant, anionic, cationic, amphoteric, or nonionic, as long as it has one allyl group, a parent group, and a hydrophobic group in one molecule. Surfactants can also be used.
具体的には、例えば、下記一般式■〜■で示される化合
物が好適に用いられる。Specifically, for example, compounds represented by the following general formulas (1) to (2) are preferably used.
■ アニオン性： ■ ノニオン性： など。■ Anionic: ■ Nonionicity: Such.
（式中、Ｘ ＝Ｎ ａ ％ Ｋ １Ｎ Ｈａなど）■
カチオン性：
ＣＨ。(In the formula, X = Na % K 1N Ha, etc.) ■
Cationicity: CH.
ＣＨ，−ＣＨ−ＣＨ，−Ｎ’″−Ｒ・Ｙ−Ｃｌ。CH, -CH-CH, -N'''-R.Y-Cl.
ＣＨ。CH.
など。Such.
（式中、￥−ＣＱ、ＣＨ，Ｃｏｏなど）など。(In the formula, ¥-CQ, CH, Coo, etc.) etc.
（式中、ｎは１以上の整数である）
上記■〜■の一般式において、ＲはいずれもＣ，〜Ｃ１
ｍのアルキル基、又はＣ，〜Ｃ１，のアルケニル基を表
わす。(In the formula, n is an integer of 1 or more) In the general formulas ■ to ■ above, R is all C, ~C1
It represents an alkyl group of m or an alkenyl group of C, to C1.
（Ｂ）成分：非水溶性架橋剤
本発明の方法で得られるエマルジョン中の微粒子状乳化
重合体の芯部を構成しうる成分であって、該エマルジョ
ン中においてその表面は後記（Ｃ）成分に基づく重合体
で被贋されており、塗装後、加熱によって各成分が溶融
し、主として（Ｂ）成分と（Ｃ）成分との架橋反応に基
いて硬化塗膜が形成される。Component (B): Water-insoluble crosslinking agent A component that can constitute the core of the particulate emulsion polymer in the emulsion obtained by the method of the present invention, and the surface of the emulsion is the component (C) described below. After coating, each component is melted by heating, and a cured coating film is formed mainly based on the crosslinking reaction between component (B) and component (C).
該（Ｂ）成分は、常温乃至重合温度において、水や（Ｃ
）成分とは反応せず、しかも水には殆どもしくは全く溶
解しないが、（Ｃ）成分とは自由に任意の割合で相溶す
るものであることが好ましい。また、（Ｂ）成分と（Ｃ
）成分との混合物は液状であって、その粘度は、該混合
物を水中に微粒子状に分散しうる範囲内であることが望
ましい。The component (B) is dissolved in water or (C) at room temperature to polymerization temperature.
It is preferable that it does not react with component (C) and has little or no solubility in water, but is freely compatible with component (C) in any proportion. In addition, component (B) and (C
It is desirable that the mixture with component ) be in a liquid state and have a viscosity within a range that allows the mixture to be dispersed in the form of fine particles in water.
（Ｂ）成分は（Ｃ）成分の乳化重合体と加熱により溶融
し架橋反応する必要があるから、該同成分は相補的に反
応して架橋結合を形成しうる官能基を相互に有している
ことが好ましい。例えば、（Ｃ）成分としてカルボキシ
ル基を有するエチレン性不飽和モノマーを使用する場合
、（Ｂ）成分としてはポリエポキシド化合物を用いるこ
とが望ましく、また、（Ｃ）成分として水酸基を有する
エチレン性不飽和モノマーを使用する場合、（Ｂ）成分
としてはポリＮ−アルコキシメチル化合物やブロック化
ポリイソシアネート化合物を用いるのが好都合である。Since component (B) needs to be melted and crosslinked with the emulsion polymer of component (C) by heating, the components must mutually have functional groups that can react complementary to each other to form a crosslinking bond. Preferably. For example, when using an ethylenically unsaturated monomer having a carboxyl group as the component (C), it is desirable to use a polyepoxide compound as the component (B), and an ethylenically unsaturated monomer having a hydroxyl group as the component (C). When using, it is convenient to use a polyN-alkoxymethyl compound or a blocked polyisocyanate compound as component (B).
勿論、（Ｂ）成分はこれらに限定されるものではなく、
他に、アルコキシシラン基含有化合物なども使用するこ
とができる。Of course, component (B) is not limited to these,
In addition, alkoxysilane group-containing compounds can also be used.
上記ポリエポキシド化合物としては次のものを例示しう
る。Examples of the above-mentioned polyepoxide compounds include the following.
■ 多価アルコールのポリグリシジルエーテル：など。■ Polyglycidyl ether of polyhydric alcohol: etc.
■ 多価フェノールのポリグリシジルエーテル；など。■Polyglycidyl ether of polyhydric phenol; etc.
■ 多価カルボン酸のポリグリシジルエーテル：など。■ Polyglycidyl ether of polyhydric carboxylic acid: etc.
■ ポリ（エポキシ化シクロへキセニル）化合物：など
。■ Poly(epoxidized cyclohexenyl) compounds: etc.
■ ポリ（エポキシ化ビニルシクロヘキセニル）化合物
：
など。■ Poly(epoxidized vinylcyclohexenyl) compounds: etc.
（ｍ％ ｎ＝１〜５）
ポリＮ−アルコキシメチル化合物としては、例えば、メ
チロール化したメラミンやベンゾグアナミンをアルコー
ルでエーテル化して得られる低分子量のものが好ましい
。(m% n=1 to 5) The poly N-alkoxymethyl compound is preferably a low molecular weight compound obtained by etherifying methylolated melamine or benzoguanamine with alcohol, for example.
ブロック化ポリイソシアネートとしては、例えば、オキ
シムでブロックされたヘキサメチレンジイソシアネート
やキシリレンジイソシアネート、インポロンジイソシア
ネートなどの脂肪族、脂環族又は芳香脂肪族系のジイソ
シアネートが好適である。As the blocked polyisocyanate, for example, aliphatic, alicyclic, or araliphatic diisocyanates such as oxime-blocked hexamethylene diisocyanate, xylylene diisocyanate, and impolon diisocyanate are suitable.
（Ｃ）成分：エチレン性不飽和七ツマー本発明において
上記（Ａ）成分および（Ｂ）成分の存在下で乳化重合せ
しめられる１分子中に少なくとも１個の重合性不飽和結
合を有するモノマーであって、この乳化重合により形成
される重合体は主に、水中に分散している微粒子状の（
Ｂ）成分の表面を被覆する。つまり、本発明の方法で得
られるエマルジョンは、水性媒体中において、（Ｂ）成
分を芯部にしてその表層は（Ｃ）成分に基づく重合体層
で被覆されている複層構造の微粒子が分散してなるもの
である。Component (C): an ethylenically unsaturated monomer having at least one polymerizable unsaturated bond in one molecule which is emulsion polymerized in the presence of the above components (A) and (B) in the present invention. The polymer formed by this emulsion polymerization is mainly composed of fine particles ((
B) Coating the surface of the component. In other words, the emulsion obtained by the method of the present invention has fine particles having a multilayer structure in which component (B) is the core and the surface layer is covered with a polymer layer based on component (C) dispersed in an aqueous medium. This is what happens.
該（Ｃ）成分は、常温乃至重合温度において水性媒体や
（Ｂ）成分と反応せず、（Ｂ）成分とは自由に任意の割
合で相溶するものであって、しかも、重合温度より高温
において、（Ｂ）成分と架橋反応しうる官能基を有する
官能性上ツマ−を含んでいることが好ましい。具体的に
は、例えば、スチレン、酢酸ビニル、（メタ）アクリル
酸アルキルエステル（例えばメタクリル酸メチル、アク
リル酸エチル、アクリル酸ｎ−ブチル、アクリル酸２−
エチルヘキシル）などの非官能性モノマー（Ｃ−１）と
、（メタ）アクリル酸などのエチレン性不飽和カルボン
酸；（メタ）アクリル酸２−ヒドロキシエチルの如き（
メタ）アクリル酸のヒドロキシアルキルエステル；（メ
タ）アクリル酸グリシジル、（メタ）アクリル酸β−（
３，４−エポキシシクロヘキシル）メチル、アリルグリ
シジルエーテルなどのエポキシ基含有不飽和上ツマ−１
Ｎ−ブトキシメチルアクリルアミドなどの官能性モノマ
ー（Ｃ−２）とを適宜組合わせて使用するのがＣＢ）成
分の架橋反応を行なわしめるために好ましい。The component (C) does not react with the aqueous medium or the component (B) at room temperature to the polymerization temperature, is freely compatible with the component (B) in any proportion, and is furthermore at a temperature higher than the polymerization temperature. It is preferable that the composition contains a functional polymer having a functional group capable of crosslinking with component (B). Specifically, examples include styrene, vinyl acetate, (meth)acrylic acid alkyl esters (such as methyl methacrylate, ethyl acrylate, n-butyl acrylate, and 2-acrylic acid).
non-functional monomers (C-1) such as (ethylhexyl) and ethylenically unsaturated carboxylic acids such as (meth)acrylic acid;
Hydroxyalkyl ester of meth)acrylic acid; glycidyl (meth)acrylate, β-(meth)acrylate
Epoxy group-containing unsaturated polymers such as 3,4-epoxycyclohexyl)methyl and allyl glycidyl ether
It is preferable to use it in appropriate combination with a functional monomer (C-2) such as N-butoxymethylacrylamide in order to carry out the crosslinking reaction of component CB).
乳化重合：
（Ａ）、（Ｂ）および（Ｃ）の各成分の構成比率は得ら
れる重合体エマルジョンに望まれる特性等に応じて任意
に選択できるが、まず、（Ｂ）成分と（Ｃ）成分とは分
散安定性等の点から固形分重量比に基いて、（Ｂ）成分
／（Ｃ）成分−５／９５〜７５／２５、中でもＩ Ｏ／
９０〜５０１５０の範囲内が好、都合であり、特に２０
／８０〜４０／６０（重量比）が好ましい。Emulsion polymerization: The composition ratio of each component (A), (B), and (C) can be arbitrarily selected depending on the desired characteristics of the resulting polymer emulsion, but first, component (B) and (C) In terms of dispersion stability, etc., the components are (B) component/(C) component - 5/95 to 75/25, based on the solid content weight ratio, especially IO/
It is preferable and convenient to have a range of 90 to 50,150, especially 20
/80 to 40/60 (weight ratio) is preferable.
また、（Ｂ）成分と（Ｃ）成分との混合物の溶解性や粘
度を調整するめだに該混合物に対し５０重量％以下の範
囲で適宜有機溶剤を加えることもできる。Further, an organic solvent may be added as appropriate to the mixture of components (B) and (C) in an amount of 50% by weight or less to adjust the solubility and viscosity of the mixture.
（Ａ）成分は、ＣＢ）成分と（Ｃ）成分との合計重量に
対し、０．２〜５重量％、中でも０．５〜３重量％で用
いるのが分散安定性及び塗膜性能等の点から好ましい。Component (A) should be used in an amount of 0.2 to 5% by weight, especially 0.5 to 3% by weight, based on the total weight of components CB) and (C) to improve dispersion stability and coating performance. Preferable from this point of view.
また、（Ｃ）成分の重合開始剤として、ベンゾイルパー
オキシド、アゾビスイソブチロニトリルなどの既知のラ
ジカル重合開始剤を使用することができる。中でも、水
溶性の過酸化水素、過硫酸アンモニウム、ｔ−ブチルハ
イドロパーオキシド、１−／チルパーオキシマレイン酸
、コハク酸パーオキシド、２．２’−アゾビス（Ｎ−ヒ
ドロキシエチルイソブチルアミド）などが好ましい。Further, as the polymerization initiator for component (C), known radical polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile can be used. Among these, water-soluble hydrogen peroxide, ammonium persulfate, t-butyl hydroperoxide, 1-/tilperoxymaleic acid, succinic acid peroxide, 2,2'-azobis(N-hydroxyethylisobutyramide), and the like are preferred.
さらに前記過酸化物に亜硫酸水素ナトリウム、チオ硫酸
ナトリウム、ヒドロキシメタンスルフィン酸ナトリウム
、第１銅塩、第１鉄塩などの還元剤を併用したレドック
ス系開始剤が有利に使用できる。Furthermore, a redox initiator in which the peroxide is combined with a reducing agent such as sodium bisulfite, sodium thiosulfate, sodium hydroxymethanesulfinate, cuprous salt, or ferrous salt can be advantageously used.
本発明の方法は、上記（Ａ）〜（Ｃ）成分を用いてそれ
自体既知の方法で乳化重合することによって行なわれる
。例えば、反応温度は（Ｂ）成分と（Ｃ）成分との反応
温度以下であり、例えば０−１００℃、特に３０〜９０
℃の範囲内が好ましく、不活性ガス雰囲気下に水相中で
、（Ａ）成分および重合開始剤の存在下に（Ｂ）成分を
含有する（Ｃ）成分を乳化重合させる。The method of the present invention is carried out by emulsion polymerization using the components (A) to (C) described above by a method known per se. For example, the reaction temperature is below the reaction temperature of component (B) and component (C), for example 0-100°C, especially 30-90°C.
The temperature is preferably within the range of 0.degree. C., and component (C) containing component (B) is emulsion polymerized in the presence of component (A) and a polymerization initiator in an aqueous phase under an inert gas atmosphere.
重合開始剤および（Ｂ）成分と（Ｃ）成分との混合物を
添加する方法としては、重合開始時に全量添加する方法
、重合の進行に従って連続的に添加する方法、一部シー
ドポリマーを作ってから添加する方法等が挙げられ、ま
た（Ａ）成分を添加する方法としては重合前に全量添加
する方法、一部を（Ｂ）＃分、（Ｃ）ｔ、分及び水とブ
レ乳化してから添加する方法等があり、適宜選択するこ
とができる。Methods for adding the polymerization initiator and a mixture of components (B) and (C) include methods of adding the entire amount at the start of polymerization, methods of adding continuously as the polymerization progresses, and methods of adding part of the mixture after making a seed polymer. In addition, methods for adding component (A) include adding the entire amount before polymerization, and adding a portion to (B) # minutes, (C) t, minutes, and after emulsifying with water. There are various methods of adding, which can be selected as appropriate.
本発明の方法で得られるエマルジョンは、例えば、水性
焼付塗料に単独で用いることができるのみならず、架橋
材含有率の高いものは他の水性樹脂分散液の硬化剤とし
ても用いることができる。The emulsion obtained by the method of the present invention can not only be used alone in, for example, a water-based baking paint, but also one with a high crosslinking material content can be used as a curing agent for other aqueous resin dispersions.
また、塗料において用いる場合のその塗装方法としては
、スプレー塗装、ロール塗装、シャワー塗装、電着塗装
、浸漬塗装等を利用することができる。Further, as a coating method when used in a paint, spray coating, roll coating, shower coating, electrodeposition coating, dipping coating, etc. can be used.
次に実施例を挙げて本発明をさらに具体的に説明するが
、本発明はこれらの実施例にのみ限定されるものではな
い。なお、部および％は原則としていずれも重量に基づ
く。EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited only to these Examples. Note that parts and percentages are basically based on weight.
実施例１
還流冷却器、撹拌期、滴下０−）、窒素導入口及び温度
計を備えたＩＱフラスコに、脱イオン水２５０ｇを仕込
み、系内を窒素ガスで置換し、水浴で７０℃に加温する
。アリル基含有アニオン界面活性剤ラムチルＳ−１８Ｏ
Ａ（花王（株）製品、５０％水溶液）２ｇおよび七−プ
チルバイトロバ〜オキシド７０％水溶液０．４ｇを仕込
み、これに下記の配合の架橋剤含有モノマー混合物ｌｏ
ｎｇ及びヒドロキシメチルスルフィン酸ナトリウム０゜
３ｇの水溶液５０ｇを別々に１時間かけて滴下する。滴
下終了後、更に７０℃で１時間熟成し、固形分２４．２
％、重合転化率９６％、平均粒径００１２μの安定なエ
マルジョンを得た。Example 1 250 g of deionized water was charged into an IQ flask equipped with a reflux condenser, stirring period, dropping (0-), nitrogen inlet, and thermometer, the system was replaced with nitrogen gas, and the temperature was heated to 70°C in a water bath. Warm up. Allyl group-containing anionic surfactant Lamutil S-18O
2 g of A (Kao Corporation product, 50% aqueous solution) and 0.4 g of a 70% aqueous solution of 7-butylbaitolova-oxide were charged, and to this was added a crosslinking agent-containing monomer mixture lo having the following composition.
ng and 50 g of an aqueous solution of 0.3 g of sodium hydroxymethylsulfinate were separately added dropwise over 1 hour. After dropping, it was further aged at 70℃ for 1 hour, and the solid content was 24.2
%, a polymerization conversion rate of 96%, and a stable emulsion with an average particle size of 0,012 μm was obtained.
配合：スチレン ２０ｇアクリル酸
ブチル ２０ｇ
メタクリル酸 １０ｇ
トリメチロールプロパン
トリグリシジルエーテル ５０ｇ
これを鋼板に塗装し、１４０℃で３０分焼付けると硬質
でしかも耐溶剤性、付着性のすぐれた塗膜が得られた。Composition: Styrene 20g Butyl acrylate 20g Methacrylic acid 10g Trimethylolpropane triglycidyl ether 50g When this is applied to a steel plate and baked at 140°C for 30 minutes, a hard coating film with excellent solvent resistance and adhesion is obtained. Ta.
実施例２
実施例１と同様なｌＱ７ラスコに脱イオン水２５０ｇを
仕込み、窒素ガスで置換後、９０℃に昇温し、アリル基
含有４級アンモニウム塩系カチオン界面活性剤、ニュー
コールＲＦ７５５（日本乳化剤（株）製品）２ｇを仕込
み、これに下記の架橋剤含有上ツマー混合液１００ｇ及
び別に水溶性アゾアミド系開始剤、ＶＡ−０８６（和光
紬薬（株）製品）０．８ｇの水溶液５０ｇを１時間かけ
て滴下し、更に９０℃で１時間熟成し、固形分２５．３
％、重合転化率９９％、平均粒径０．０８μの安定なエ
マルジョンを得た。Example 2 250 g of deionized water was placed in a lQ7 flask similar to Example 1, and after purging with nitrogen gas, the temperature was raised to 90°C, and allyl group-containing quaternary ammonium salt cationic surfactant, Nucor RF755 (Japan) 2 g of Emulsifier Co., Ltd. product) was charged, and to this was added 100 g of the following crosslinking agent-containing mixture and 50 g of an aqueous solution of 0.8 g of a water-soluble azoamide initiator, VA-086 (Wako Tsumugi Co., Ltd. product). Dropped over 1 hour, further aged at 90℃ for 1 hour, solid content 25.3
%, a polymerization conversion rate of 99%, and a stable emulsion with an average particle size of 0.08 μm were obtained.
配合：スチレン ４８ｇアクリル酸
２−エチルヘキシル２０ｇ
メタクリル酸 １２ｇ
ヘキサンカルボキシレート ２０ｇ
これをブリキ板に塗布し、１６０°０で２０分焼付ける
と硬くて耐溶剤性のあるフィルムが得られた。Blend: 48 g of styrene, 20 g of 2-ethylhexyl acrylate, 12 g of methacrylic acid, 20 g of hexane carboxylate This was applied to a tin plate and baked at 160°0 for 20 minutes to obtain a hard, solvent-resistant film.
実施例３
実施例１と同様なｔｃフラスコに脱イオン水３５０ｇを
仕込み、窒素ガスで置換後、７０°Ｃに昇温し、アリル
基含有アニオン界面活性剤、５０％ラムチルＳ５−１８
ＯＡ４及び同ノニオン界面活性剤ノイゲンＨ−３３５５
Ｎ（第一工業製薬（株）製品）Ｉｇ、及びｔ−ブチルハ
イドロパーオキシド７０％水溶液０．５ｇを仕込み、こ
れに下記の配合の架橋剤含有七ツマー混金物１００部及
びヒドロキシメチルスルフィン酸ナトリウム０．３の水
溶液５０ｇを別々に４０分間かけて滴下し、更に７０℃
で９０分間熟成して、固形分１９．７％、重合転化率９
７％、平均粒径０．２０μの安定なエマルジョンを得た
。Example 3 350 g of deionized water was charged into a TC flask similar to that in Example 1, and after purging with nitrogen gas, the temperature was raised to 70°C, and allyl group-containing anionic surfactant, 50% Ramuthyl S5-18 was added.
OA4 and its nonionic surfactant Neugen H-3355
N (product of Daiichi Kogyo Seiyaku Co., Ltd.) Ig and 0.5 g of a 70% aqueous solution of t-butyl hydroperoxide were charged, and to this was added 100 parts of a heptamine mixture containing a crosslinking agent and sodium hydroxymethyl sulfinate having the following composition. 0.3 aqueous solution was separately added dropwise over 40 minutes, and further heated to 70°C.
Aged for 90 minutes, solid content 19.7%, polymerization conversion rate 9.
A stable emulsion of 7% and an average particle size of 0.20μ was obtained.
配合：メタクリル酸メチルン ４０ｇアクリル酸
２−エチルヘキシル３０ｇ
アクリル酸 １０ｇ
ビスフェノールＡ ジグリシ
ジルエーテル ２０ｇ
これにトリエチルアミン２部加え、クロム酸処理亜鉛メ
ツキ鋼板にスプレー塗装し、１３０℃で２０分焼付ける
と、耐溶剤性のある付着性の良い塗膜が得られた。Blend: 40 g of methyl methacrylate 30 g of 2-ethylhexyl acrylate 10 g of acrylic acid 20 g of bisphenol A diglycidyl ether Add 2 parts of triethylamine to this, spray paint on a chromic acid-treated galvanized steel sheet, and bake at 130°C for 20 minutes to make it solvent resistant. A coating film with good adhesion was obtained.
実施例４
実施例１と同様のｌＱ７ラスコに、脱イオン水２５０ｇ
を仕込み、系内を窒素ガスで置換し、水浴で６０℃に加
温する。スルホコハク酸アリルエステル系アニオン界面
活性剤、ラムチルｓ−ｔｇＯＡ（花王（株）製品）５０
％水溶液４ｇ及びｔ−ブチルハイドロパーオキシド７０
％水溶液０．５ｇを仕込み、これに下記の配合の架橋剤
含有七ツマー混合物ｌＯＯ部及び亜硫酸水素アンモニウ
ム０，２５ｇの水溶液５０ｇを別々に１時間かけて滴下
し、更に６０℃で２時間熟成し、固形分２５．１％、重
合転化率９９％、平均粒径０．１７μのエマルジョンを
得た。Example 4 In a lQ7 flask similar to Example 1, add 250 g of deionized water.
The system was purged with nitrogen gas and heated to 60°C in a water bath. Sulfosuccinic acid allyl ester anionic surfactant, Ramuthyl s-tgOA (Kao Corporation product) 50
% aqueous solution 4 g and t-butyl hydroperoxide 70
% aqueous solution, 100 parts of a 7-mer mixture containing a crosslinking agent with the following composition and 50 g of an aqueous solution of 0.25 g of ammonium bisulfite were separately added dropwise over 1 hour, and further aged at 60°C for 2 hours. An emulsion having a solid content of 25.1%, a polymerization conversion rate of 99%, and an average particle size of 0.17 μm was obtained.
配合：スチレン ３０ｇアクリル酸
ｎ−ブチル ２５ｇ
メタクリル酸２−ヒドロキシ
エチル １７ｇ
ミカル（株）製品） ２５ｇこれをブリキ
板にスプレー塗装し、１７０℃で２０分焼付けると、硬
くて耐溶剤性のある塗膜が得られた。Blend: Styrene 30g n-butyl acrylate 25g 2-hydroxyethyl methacrylate 17g Michal Co., Ltd. product) 25g Spray paint on a tin plate and bake at 170°C for 20 minutes to create a hard, solvent-resistant coating. A membrane was obtained.
実施例５
実施例４と同様の操作で下記の配合の架橋剤含有モノマ
ー混合物を乳化重合して、固形分２０゜５％、重合転化
率１００％、平均粒径０．２０μのエマルジョンヲ得り
。Example 5 A monomer mixture containing a crosslinking agent having the following composition was emulsion polymerized in the same manner as in Example 4 to obtain an emulsion with a solid content of 20.5%, a polymerization conversion rate of 100%, and an average particle size of 0.20μ. .
配合：スチレン ２５ｇアクリル酸
２−エチルヘキ
シル ２５ｇアクリル酸２−
ヒドロキシ
エチル ２０ｇ
アクリル厳
ｇ
（日立化ＴＲ（株）製品） ４０ｇ実施例６
実施例１と同様なＩＱ７ラスコに脱イオン水３００ｇを
仕込み、窒素ガスで置換後、８０℃に昇温し、アリル基
含有４級アンモニウム塩系カチオン界面活性剤、ラムチ
ルに一１８０Ａｃ（花王（株）製品）３ｇを仕込み、こ
れに下記の重合開始剤及び架橋剤含有モノマー混合物１
０１ｇを１時間かけて滴下し、更に７０℃で２時間熟成
して、固形分２４．９％、重合転化率９９％、平均粒径
０．２１μの安定なエマルジョンを得た。Composition: Styrene 25g 2-ethylhexyl acrylate 25g acrylic acid 2-
Hydroxyethyl 20g Acrylic acid g (Product of Hitachi Chemical TR Co., Ltd.) 40g Example 6 300g of deionized water was charged into an IQ7 flask similar to that in Example 1, and after purging with nitrogen gas, the temperature was raised to 80°C to remove allyl groups. A quaternary ammonium salt-based cationic surfactant containing 3 g of 1180Ac (manufactured by Kao Corporation) was added to Ramuthyl, and the following monomer mixture containing a polymerization initiator and crosslinking agent 1 was added to it.
01g was added dropwise over 1 hour and further aged at 70°C for 2 hours to obtain a stable emulsion with a solid content of 24.9%, a polymerization conversion rate of 99%, and an average particle size of 0.21μ.
配合：スチレン
０ｇ
アクリル酸ｎ−ブチル
０ｇ
キシム付加物 ２０ｇ
ジブチル錫ジラウレート ０．５ｇｔ−ブチルハイ
ドロパーオキ
シド ０．５ｇこれをブリキ板
にスプレー塗装し、１６０℃で２０分間焼付けると、柔
軟で耐溶剤性のある塗膜を得た。Blend: 0 g of styrene, 0 g of n-butyl acrylate, 20 g of xime adduct, 0.5 g of dibutyltin dilaurate, 0.5 g of t-butyl hydroperoxide, and when spray-painted on a tin plate and baked at 160°C for 20 minutes, it becomes flexible and solvent-resistant. A coating film with good properties was obtained.
比較例１
実施例１において界面活性剤をアリル基不含のニューコ
ール２７１Ａ（日本乳化剤（株）製）に置き換えると、
架橋剤とモノマーとの混合物を約１／。Comparative Example 1 When the surfactant in Example 1 was replaced with allyl group-free Nucor 271A (manufactured by Nippon Nyukazai Co., Ltd.),
The mixture of crosslinking agent and monomer is about 1/1.
滴下した時、凝集した。When added dropwise, it aggregated.
比較例２．６
実施例２．６において界面活性剤をアリル基不含のコー
タミン８６Ｐ（花王（株）製）に置き換ると、ともに重
合後一部沈降した。Comparative Example 2.6 When the surfactant in Example 2.6 was replaced with allyl group-free Cortamine 86P (manufactured by Kao Corporation), some sedimentation occurred after polymerization.
比較例３
実施例３において界面活性剤をアリル基不含のネオゲン
Ｒ及製びノイゲンＥＡ−１２０（ともに第一工業製薬（
株）製）に置き換えると、重合後分離した。Comparative Example 3 In Example 3, the surfactants were Allyl group-free Neogen R and Neugen EA-120 manufactured by Daiichi Kogyo Seiyaku (both Daiichi Kogyo Seiyaku).
Co., Ltd.), it separated after polymerization.
比較例４．５
重合体４．５においてアリル基不含のニューコール７０
７５Ｆ（日本乳化剤（株）製）に置き換えると、ともに
重合体中多量の凝集物を生じた。Comparative Example 4.5 Nucor 70 without allyl groups in Polymer 4.5
When it was replaced with 75F (manufactured by Nippon Nyukazai Co., Ltd.), a large amount of aggregates were formed in both polymers.
Claims (4)
性架橋剤の存在下に（Ｃ）エチレン性不飽和モノマーを
乳化重合させることを特徴とする架橋剤含有乳化重合体
エマルジョンの製造方法。(1) A crosslinking agent-containing emulsion polymer emulsion characterized in that (C) an ethylenically unsaturated monomer is emulsion polymerized in the presence of (A) an allyl group-containing surfactant and (B) a water-insoluble crosslinking agent. Production method.
に対して０．５〜３．０重量％の範囲内で使用する請求
項１記載の方法。(2) The method according to claim 1, wherein component (A) is used in an amount of 0.5 to 3.0% by weight based on the total amount of components (B) and (C).
）成分がカルボキシル基を有するモノマーを含むことを
特徴とする請求項１又は２記載の方法。(3) Component (B) is a polyepoxide compound, and (C
3. The method according to claim 1, wherein component ) contains a monomer having a carboxyl group.
はブロック化ポリイソシアネート化合物であり、（Ｃ）
成分がヒドロキシル基を有するモノマーを含むことを特
徴とする請求項１又は２記載の方法。(4) Component (B) is a poly N-alkoxymethyl compound or a blocked polyisocyanate compound, and (C)
3. A method according to claim 1 or 2, characterized in that the component comprises a monomer having hydroxyl groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7042889A JPH02251502A (en) | 1989-03-24 | 1989-03-24 | Preparation of crosslinking agent-containing emulsified polymer emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7042889A JPH02251502A (en) | 1989-03-24 | 1989-03-24 | Preparation of crosslinking agent-containing emulsified polymer emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02251502A true JPH02251502A (en) | 1990-10-09 |
Family
ID=13431201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7042889A Pending JPH02251502A (en) | 1989-03-24 | 1989-03-24 | Preparation of crosslinking agent-containing emulsified polymer emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02251502A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231616A (en) * | 1994-12-27 | 1996-09-10 | Asahi Chem Ind Co Ltd | Curable water-based resin composition |
| JP2003526709A (en) * | 1999-12-11 | 2003-09-09 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Aqueous primary dispersion and coating material, process for its preparation and its use |
| WO2020100790A1 (en) * | 2018-11-13 | 2020-05-22 | 昭和電工株式会社 | Aqueous resin emulsion, method for producing same, and aqueous resin composition |
| JP2023036025A (en) * | 2021-09-01 | 2023-03-13 | ハンナノテク カンパニー，リミテッド | Quenching agent containing emulsion polymer particles, quenching polymer composition comprising the same and method for producing the same |
-
1989
- 1989-03-24 JP JP7042889A patent/JPH02251502A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231616A (en) * | 1994-12-27 | 1996-09-10 | Asahi Chem Ind Co Ltd | Curable water-based resin composition |
| JP2003526709A (en) * | 1999-12-11 | 2003-09-09 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Aqueous primary dispersion and coating material, process for its preparation and its use |
| WO2020100790A1 (en) * | 2018-11-13 | 2020-05-22 | 昭和電工株式会社 | Aqueous resin emulsion, method for producing same, and aqueous resin composition |
| CN112703207A (en) * | 2018-11-13 | 2021-04-23 | 昭和电工株式会社 | Aqueous resin emulsion, process for producing the same, and aqueous resin composition |
| JPWO2020100790A1 (en) * | 2018-11-13 | 2021-09-02 | 昭和電工株式会社 | Aqueous resin emulsion and its production method, and aqueous resin composition |
| CN112703207B (en) * | 2018-11-13 | 2024-03-12 | 株式会社力森诺科 | Aqueous resin emulsion, method for producing same, and aqueous resin composition |
| JP2023036025A (en) * | 2021-09-01 | 2023-03-13 | ハンナノテク カンパニー，リミテッド | Quenching agent containing emulsion polymer particles, quenching polymer composition comprising the same and method for producing the same |
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