JPH02300204A - Production of reactive microgel - Google Patents
Production of reactive microgelInfo
- Publication number
- JPH02300204A JPH02300204A JP12186789A JP12186789A JPH02300204A JP H02300204 A JPH02300204 A JP H02300204A JP 12186789 A JP12186789 A JP 12186789A JP 12186789 A JP12186789 A JP 12186789A JP H02300204 A JPH02300204 A JP H02300204A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polymer particles
- vinyl
- vinyls
- seed polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 abstract description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract 1
- 239000003995 emulsifying agent Substances 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920003169 water-soluble polymer Polymers 0.000 description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- -1 vinyl compound Chemical class 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- VAPKHDZBJXRVNG-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene;1-ethenyl-4-methylbenzene Chemical group CC1=CC=C(C=C)C=C1.CC1=CC=CC(C=C)=C1 VAPKHDZBJXRVNG-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical class [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ポリマー粒子の数平均粒子径を１０〜１１０
０ｎの範囲で自由にコントロールでき、かつ粒子表面に
未反応ビニル基を多く含む反応性ミクロゲルの新規な製
造方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention is directed to polymer particles having a number average particle diameter of 10 to 110.
The present invention relates to a novel method for producing reactive microgels that can be freely controlled within the 0n range and that contain many unreacted vinyl groups on the particle surface.
［従来の技術］
従来、５０ｎｓ以下の粒子径を有し、かつ架橋されたポ
リマー粒子を乳化重合法により合成した水性分散体はミ
クロゲルと呼ばれ、その有用性が検討されている。[Prior Art] Conventionally, an aqueous dispersion prepared by emulsion polymerization of crosslinked polymer particles having a particle size of 50 ns or less is called a microgel, and its usefulness has been studied.
例えば、文献Ｊ、 Ｏｆｔ Ｃｏ１． Ｃｈｅｗ、＾５
ｓｏｃ、、 ６０゜４３８（１９７７）に記載されてい
るように、ミクロゲルをポリスチレン樹脂中や不飽和ポ
リエステル中に分散させ、これを補強剤として応用する
ことなどが示されている。これは、ミクロゲルのポリマ
ー粒子表面における反応性に富むペンダントビニル基が
マトリックスである樹脂にグラフトして補強効果を発揮
するものと考えられる。For example, Document J, Of Co1. Chew, ^5
Soc, 60° 438 (1977), it has been shown that microgels are dispersed in polystyrene resins or unsaturated polyesters and used as reinforcing agents. This is thought to be due to the highly reactive pendant vinyl groups on the surface of the microgel polymer particles grafting onto the matrix resin to exert a reinforcing effect.
また、染料や医薬、農薬などをミクロゲルのポリマー粒
子表面に固定化することも考えられてぃる。It is also possible to immobilize dyes, medicines, agricultural chemicals, etc. on the surface of microgel polymer particles.
［発明が解決しようとする問題点］
このように反応性ミクロゲルの用途としては、従来のラ
テックスにない新しい分野が期待されるが、製造上次の
ような問題点がある。[Problems to be Solved by the Invention] As described above, reactive microgels are expected to be used in new fields not found in conventional latex, but they have the following problems in production.
まず第１の問題点としては、ポリマー粒子として粒子径
が最大５０１１１％通常４０ｎ＊以り程度のものしか得
られない点である。これ以上の粒子径のものを得ようと
すると、２００〜５００ｎ−の大きな粒子径であって不
定形かつ粒子径分布の非常に広いものしか得られなかっ
た。５０〜１００ ｎｕの範囲でポリマー粒子の粒子径
をコントロールすることは、前記文献Ｊ、 Ｏｌｌ Ｃ
ｏｔ、 Ｃｈｅｗ、 Ａｓ５ｏｅ、。The first problem is that only polymer particles with a maximum particle diameter of 50111% and usually 40n* or more can be obtained. When trying to obtain particles with a larger particle size, only large particles with a large particle size of 200 to 500 n-, irregular shapes, and a very wide particle size distribution were obtained. Controlling the particle size of polymer particles in the range of 50 to 100 nu is described in the above-mentioned document J, Oll C
ot, Chew, As5oe,.
６０、４３８ （１９７７）および表面Ｖｏ１．２５
Ｎｏ、２８８ （１９８７）に示されたように、従来に
おいては技術的に不可能であった。60, 438 (1977) and Surface Vol. 1.25
No. 288 (1987), this was technically impossible in the past.
第２の問題点としては、合成において非常に多量の乳化
剤を必要とする点である。この乳化剤は、ミクロゲルの
各種用途において好ましくない影響を与えることが考ら
れる。The second problem is that the synthesis requires a very large amount of emulsifier. This emulsifier is considered to have an unfavorable effect on various uses of microgels.
さらに第３の問題点としては、反応性ミクロゲルの合成
には、多量の架橋性モノマーを必要とする点である。一
般に架橋性モノマーは非架橋性上ツマ−と比較して高価
であり、このため製品コストが高くなり、用途範囲が限
定されるという難点があった。A third problem is that synthesis of reactive microgels requires a large amount of crosslinking monomer. Generally, crosslinking monomers are more expensive than non-crosslinking monomers, resulting in higher product costs and a limited range of applications.
このように、粒子径が１０〜１０１００ｎで、かつ乳化
剤濃度が低くても安定性の良い高架橋ラテックスである
反応性ミクロゲルを合成する技術は、従来知られていな
かった。As described above, a technique for synthesizing a reactive microgel, which is a highly crosslinked latex with a particle size of 10 to 10100 nm and good stability even at a low emulsifier concentration, has not been previously known.
本発明は、このような背景の下になされたものであり、
その目的は、１０〜１１００ｎの範囲で自由に粒子径コ
ントロールができ、比較的低濃度の乳化剤の存在下で安
定性良く重合を行うことができ、さらに架橋性モノマー
のモノマー全体に対する使用量を反応性を低下させるこ
となく減少させてコストの低減を図ることが可能な新規
な反応性ミクロゲルの製造方法を提供することにある。The present invention was made against this background,
The purpose of this is to be able to freely control the particle size in the range of 10 to 1100 nm, to perform polymerization with good stability in the presence of a relatively low concentration of emulsifier, and to control the amount of crosslinking monomers used based on the total monomers. The object of the present invention is to provide a novel method for producing a reactive microgel, which can reduce the cost without reducing the properties.
［問題点を解決するための手段］
本発明は、下記の第１工程および第２工程を含むことを
特徴とする、数平均粒子径が１０〜１００ｎｉで粒子表
面にビニル基を有する反応性ミクロゲルの製造方法に関
する。[Means for Solving the Problems] The present invention provides a reactive microgel having a number average particle diameter of 10 to 100 ni and having vinyl groups on the particle surface, which is characterized by comprising the following first step and second step. Relating to a manufacturing method.
第１工程；
ビニル基を２以上有する架橋性モノマーを５．５重量％
以下の割合で含有するビニル系モノマーを乳化重合し、
数平均粒子径が５〜８０ｎｓであるシードポリマー粒子
を合成する工程。1st step; 5.5% by weight of crosslinkable monomer having 2 or more vinyl groups
Emulsion polymerization of vinyl monomers contained in the following proportions,
A step of synthesizing seed polymer particles having a number average particle diameter of 5 to 80 ns.
第２工程；
第１工程で得られたシードポリマー粒子５〜１０００重
量部（固形分）の存在下において、ビニル基を２以上有
する架橋性モノマーを６重量％以上含有するビニル系モ
ノマー１００重量部を乳化重合する工程。 。Second step: In the presence of 5 to 1000 parts by weight (solid content) of the seed polymer particles obtained in the first step, 100 parts by weight of a vinyl monomer containing 6% by weight or more of a crosslinkable monomer having two or more vinyl groups The process of emulsion polymerization. .
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の第１工程で用いられる架橋性上ツマ−としては
、ジビニルベンゼン、エチレングリコールジメタクリレ
ート、１，３−ブチレングリコールジメタクリレート、
トリメチロールブロバントリメタタリ・レート、トリメ
ナロールエタントリメタクリレート、ネオペンチルグリ
コールジメタクリレート、メチレンビスアクリルアミド
を例示することができ、特にジビニルベンゼン、エチレ
ングリコールジメタクリレートが好ましい。これらは２
種以上を組みあわせて使用してもよい。The crosslinking materials used in the first step of the present invention include divinylbenzene, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
Examples include trimethylolbroban trimethacrylate, trimenalolethane trimethacrylate, neopentyl glycol dimethacrylate, and methylene bisacrylamide, with divinylbenzene and ethylene glycol dimethacrylate being particularly preferred. These are 2
You may use a combination of more than one species.
本発明においては、第１工程における架橋性モノマーの
使用割合は、第１工程で用いられる全モノマーに対して
５．５重量％以下、好ましくは３重量％以下とすること
が必要であり、また重合安定性との関係で架橋性上ツマ
−を全く使用しなくてもよい。In the present invention, it is necessary that the proportion of the crosslinkable monomer used in the first step is 5.5% by weight or less, preferably 3% by weight or less, based on the total monomers used in the first step, and In view of polymerization stability, it is not necessary to use any crosslinking additives at all.
なお、工業用に架橋性モノマーとして用いられるものの
中には、ビニル基を１つしか有さないモノマーや、ビニ
ルモノマー以外の溶剤が含まれる場合があるので、前述
した架橋性モノマーの使用割合は有効成分であるビニル
基を２個以上有する七ツマー成分のみを基準とする。In addition, some of the crosslinking monomers used for industrial purposes may include monomers having only one vinyl group or solvents other than vinyl monomers, so the usage ratio of the crosslinking monomers mentioned above may vary. Only heptamer components having two or more vinyl groups, which are active ingredients, are used as standards.
本発明の第１工程において、前記架橋性モノマーと共に
用いられる非架橋性重合性モノマーとしては、スチレン
、α−メチルスチレン、フルオロスチレン、ビニルピリ
ジンなどの芳香族モノビニル化合物、アクリロニトリル
、メタクリレートリルなどのシアン化ビニル化合物、ブ
チルアクリレート、２−エチルへキシルアクリレート、
メチルアクリレート、２−ヒドロキシエチルアクリレー
ト、グリシジルアクリレート、Ｎ、Ｎ’ −ジメチル
アミノエチルアクリレートなどのアクリル酸エステルモ
ノマー、ブチルメタクリレート、２−エチルへキシルメ
タクリレート、メチルメタクリレート、２−ヒドロキシ
エチルメタクリレート、グリシジルメタクリレート、Ｎ
、Ｎ’ −ジメチルアミノエチルメタクリレートなど
のメタクリル酸エステルモノマー、アクリル酸、メタク
リル酸、マレイン酸、イタコン酸などのモノまたはジカ
ルボン酸およびジカルボン酸の酸無水物、アクリルアミ
ド、メタクリルアミドなどのアミド系モノマー、さらに
スチレンスルホン酸ナトリウム、スルホン化イソプレン
などのイオン性モノマーなどを用いることができる。ま
た重合速度および重合安定性の点で許容される範囲内に
おいて、ブタジェン、イソプレンなどの共役二重結合化
合物や酢酸ビニルなどのビニルエステル化合物、４−メ
チル−１−ペンテン、その他のα−オレフィン化合物ｔ
、使用することができる。In the first step of the present invention, the non-crosslinkable polymerizable monomer used together with the crosslinkable monomer includes aromatic monovinyl compounds such as styrene, α-methylstyrene, fluorostyrene, and vinylpyridine, and cyanogen compounds such as acrylonitrile and methacrylate. vinyl compound, butyl acrylate, 2-ethylhexyl acrylate,
Acrylic acid ester monomers such as methyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, N,N'-dimethylaminoethyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, N
, methacrylic acid ester monomers such as N'-dimethylaminoethyl methacrylate, mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and acid anhydrides of dicarboxylic acids, amide monomers such as acrylamide and methacrylamide, Furthermore, ionic monomers such as sodium styrene sulfonate and sulfonated isoprene can be used. In addition, within the allowable range in terms of polymerization rate and polymerization stability, conjugated double bond compounds such as butadiene and isoprene, vinyl ester compounds such as vinyl acetate, 4-methyl-1-pentene, and other α-olefin compounds. t
, can be used.
また、本発明の第１工程において用いられる分子量調整
剤としては、例えばｔ−ドデシルメルカプタン、オクチ
ルメルカプタン、ｎ−テトラデシルメルカプタン、ｔ−
へキシルメルカプタン、ｎ−へキシルメルカプタン等の
メルカプタン類、四塩化炭素、臭化エチレン等のハロゲ
ン系化合物などを使用することができる。Further, as the molecular weight regulator used in the first step of the present invention, for example, t-dodecylmercaptan, octylmercaptan, n-tetradecylmercaptan, t-
Mercaptans such as hexyl mercaptan and n-hexyl mercaptan, halogen compounds such as carbon tetrachloride and ethylene bromide, etc. can be used.
本発明の第１工程において用いられる乳化剤としては、
通常の乳化重合で使用されるものを用いることができ、
ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸
ナトリウム、ジアルキルスルホコハク酸ナトリウム、ナ
フタレンスルホン酸のホルマリン縮合物、ポリオキシエ
チレンアルキルフェニルエーテルサルフェートアンモニ
ウム塩などのアニオン系界面活性剤を例示することがで
き、さらにポリオキシエチレンノニルフェニルエー・チ
ル、ポリエチレングリコールモノステアレート、ソルビ
タンモノステアレートなどのノニオン系界面活性剤を例
示することができる。As the emulsifier used in the first step of the present invention,
Those used in ordinary emulsion polymerization can be used,
Examples of anionic surfactants include sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium dialkyl sulfosuccinate, formalin condensate of naphthalene sulfonic acid, polyoxyethylene alkylphenyl ether sulfate ammonium salt, and polyoxyethylene. Examples include nonionic surfactants such as nonylphenylethyl, polyethylene glycol monostearate, and sorbitan monostearate.
さらに、市販の乳化剤であるニューフロンティアＡ−２
２９Ｅ、同Ｎ１７７Ｅ、同Ｎ２５０Ｚ。Furthermore, New Frontier A-2, a commercially available emulsifier,
29E, N177E, N250Z.
同Ｎ２８０．同Ｎ１２１Ｐ （第−工業製薬鞠製）やエ
レミノールＪＳ−２，同Ｒ３−３０（三洋化成工業■製
）などを使用することもできる。Same N280. Eleminol N121P (manufactured by Dai-Kogyo Seiyaku Mari), Eleminor JS-2, Eleminor R3-30 (manufactured by Sanyo Chemical Industries, Ltd.), etc. can also be used.
これら乳化剤としては、１種類でもよいが２種類以上を
組み合せて使用すれば、さらに安定性の点で効果がある
。さらに好ましい組み合せとしては、アニオン系界面活
性剤とノニオン系界面活性剤との組み合せがある。Although one type of these emulsifiers may be used, a combination of two or more types is more effective in terms of stability. A more preferable combination is a combination of an anionic surfactant and a nonionic surfactant.
乳化剤の使用量は、通常の乳化重合粒子よりも粒子径が
小さく粒子表面積が大きいことがら、通常の乳化重合よ
り多量に必要とし、全モノマーに対し好ましくは１０重
量％以上、さらに好ましくは２０重量％以上とされる。The amount of emulsifier used is smaller than that of ordinary emulsion polymerization particles and has a larger particle surface area, so a larger amount is required than in ordinary emulsion polymerization, and is preferably 10% by weight or more, more preferably 20% by weight based on the total monomers. % or more.
また、本発明の第１工程においては、水溶性高分子を乳
化剤と併用してもよい。Furthermore, in the first step of the present invention, a water-soluble polymer may be used in combination with an emulsifier.
水溶性高分子の具体例としては、ポリビニルアルコール
、デキストリン、ヒドロキシエチルデンプン、ヒドロキ
シエチルセルロース、ヒドロキシプロピルセルロースお
よびポリアクリル酸やスチレンアクリル酸共重合物など
のナトリウム塩、縮合ナフタレンスルホン酸ナトリウム
塩などを挙げることができ、これらは全モノマーに対し
好まＬ２くは１〜３０重量％、さらに好ましくは３＝２
０重量％使用されるのが適当である。Specific examples of water-soluble polymers include polyvinyl alcohol, dextrin, hydroxyethyl starch, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium salts of polyacrylic acid and styrene acrylic acid copolymers, and condensed naphthalene sulfonic acid sodium salts. These are preferably L2 or 1 to 30% by weight based on the total monomers, more preferably 3=2
Suitably, 0% by weight is used.
本発明の第１工程で使用される重合開始剤としては、通
常の乳化重合で用いられるものであれば特に制限されな
いが、過硫酸カリウム、過硫酸ナトリウム、過硫酸アン
モニウム等の過硫酸塩系開始剤、および過酸化水素、有
機過酸化物等を単独であるいはアスコルビン酸等の各種
還元剤と組み合せて使用してもよい。The polymerization initiator used in the first step of the present invention is not particularly limited as long as it is used in ordinary emulsion polymerization, but persulfate initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, etc. , hydrogen peroxide, organic peroxides, etc. may be used alone or in combination with various reducing agents such as ascorbic acid.
本発明の第１工程で使用される水の量は、七ツマ−に対
し好ましくは２００重量％以上１、さらに好ましくは３
００重量％以上である。The amount of water used in the first step of the present invention is preferably 200% or more by weight1, more preferably 3% by weight based on the amount of water.
00% by weight or more.
以上説明した第１工程においては、数平均粒子径が５〜
８０ｎｍで、粒子径のコントロールが容易なシードポリ
マー粒子が得られる。In the first step explained above, the number average particle diameter is 5 to
At 80 nm, seed polymer particles whose particle size can be easily controlled can be obtained.
本発明の第２工程においては、架橋性モノマーを６重量
％以上含有するビニル系モノマー１００重量部を乳化重
合するにあたり、第１工程で得られたポリマー粒子をシ
ードポリマー粒子として５〜１０００重量部（固形分）
、好ましくは１０〜５００重量部使用することが必要で
ある。In the second step of the present invention, when emulsion polymerizing 100 parts by weight of a vinyl monomer containing 6% by weight or more of a crosslinkable monomer, 5 to 1000 parts by weight of the polymer particles obtained in the first step are used as seed polymer particles. (solid content)
, preferably 10 to 500 parts by weight.
シードポリマー粒子が５重量部より少ないと、２００
ｎ＊以上の粗大粒子が発生しやすく、重合安定性が低下
し、また結果的に架橋性モノマーを多く使用することに
なって、製品コストの面でも好ましくない。一方、シー
ドポリマー粒子が１０００重量部より多いと、ポリマー
中の架橋部分の割合が低下し、粒子の強度および表面の
反応性の点で好ましくなく、さらに乳化剤を減する効果
も期待できない。If the seed polymer particles are less than 5 parts by weight, 200
Coarse particles of n* or more are likely to be generated, polymerization stability is reduced, and as a result, a large amount of crosslinking monomer is used, which is undesirable in terms of product cost. On the other hand, if the amount of seed polymer particles is more than 1000 parts by weight, the proportion of crosslinked parts in the polymer will decrease, which is unfavorable in terms of particle strength and surface reactivity, and furthermore, the effect of reducing the amount of emulsifier cannot be expected.
本発明の第２工程において用いられる架橋性上ツマ−の
使用割合は、第２工程で用いられるモノマー全体に対し
６重量％以上、好ましくは１０重量％以上、さらに好ま
しくは２０重量％以上である。架橋性モノマーの使用割
合が６重量％未満であると、粒子表面にビニル基がほと
んど存在しないことになり、粒子表面における反応性が
不十分となる。The proportion of the crosslinking polymer used in the second step of the present invention is 6% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more based on the total monomers used in the second step. . If the proportion of the crosslinking monomer used is less than 6% by weight, almost no vinyl groups will be present on the particle surface, resulting in insufficient reactivity on the particle surface.
架橋性モノマーおよびそれと共に用いられる非架橋性上
ツマ−の種類としては、第１工程において例示したもの
を同様に使用することができる。As for the crosslinkable monomer and the non-crosslinkable monomer used therewith, those exemplified in the first step can be used in the same manner.
第２工程において、シードポリマー粒子の存在下にモノ
マーを添加する方法としては、一括添加。In the second step, the monomer is added in the presence of the seed polymer particles by bulk addition.
連続的添加または間欠的添加、あるいはこれらの組合せ
のいずれでもよい。It may be added continuously or intermittently, or a combination thereof.
本発明の第２工程においては、乳化剤または水溶性高分
子を全く添加しなくともよく、結果的に反応性ミクロゲ
ルにおける乳化剤あるいは水溶性高分子の含有量を従来
の反応性ミクロゲルに比較して大幅に減することができ
る。ただし、重合安定性をより高度に維持させるため、
第１工程において例示した乳化剤または水溶性高分子を
必要に応じて少量だけ追加添加してもよい。In the second step of the present invention, it is not necessary to add any emulsifier or water-soluble polymer, and as a result, the content of emulsifier or water-soluble polymer in the reactive microgel can be significantly increased compared to conventional reactive microgels. can be reduced to However, in order to maintain a higher degree of polymerization stability,
The emulsifier or water-soluble polymer exemplified in the first step may be additionally added in a small amount as necessary.
また、重合開始剤についても、第１工程において例示し
たものを適宜使用すればよい。Furthermore, as for the polymerization initiator, those exemplified in the first step may be used as appropriate.
また、水の量は、最終ミクロゲルが重合中に凝集融着し
ない条件であれば特に制限されないが、第２工程で用い
られる全ポリマーに対し好ましくは３００重量％以上、
さらに好ましくは４００重量％以上である。The amount of water is not particularly limited as long as the final microgel does not aggregate and fuse during polymerization, but it is preferably 300% by weight or more based on the total polymer used in the second step.
More preferably, it is 400% by weight or more.
このように第１工程および第２工程を経ることにより、
粒子径が小さく、粒子表面にビニル基を多く有する反応
性ミクロゲルを効率よく合成することができる。すなわ
ち、本発明で定義する反応性ミクロゲルとは、数平均粒
子径が１０〜１００ｎｌであり、残留ペンダントビニル
基の量がポリマー固形分１００ｇに対し１０ミリモル以
上のものである。By going through the first and second steps in this way,
A reactive microgel having a small particle size and many vinyl groups on the particle surface can be efficiently synthesized. That is, the reactive microgel defined in the present invention has a number average particle diameter of 10 to 100 nl, and the amount of residual pendant vinyl groups is 10 mmol or more per 100 g of polymer solid content.
上記ペンダントビニル基の定量方法はどのような方法で
も良いが、例えばフーリエ変換赤外分光装置を使用する
ことができる。Any method may be used to quantify the pendant vinyl group, but for example, a Fourier transform infrared spectrometer can be used.
本発明で示した製造方法により始めて上記反応性ミクロ
ゲルを工業的規模で製造することができるようになった
。The above-mentioned reactive microgel can now be produced on an industrial scale for the first time by the production method shown in the present invention.
［実施例］
以下、本発明を実施例によってさらに具体的に説明する
が、本発明はこれらの実施例によってなんら制限される
ものではない。なお、以下の記載において、「部」およ
び「％」は重量部および重量％を意味する。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, in the following description, "part" and "%" mean parts by weight and weight %.
実施Ｍｌ〜６．比較例１〜７
（１）第１１程；シードポリマー粒子の合成第１表に示
す組成のモノマー、連鎖移動剤、乳化剤およびイオン交
換水を内容積１００！のステンレス製反応容器に仕込み
、さらに系の温度を７０℃まで上昇させ、この状態で第
１表に示す重合開始剤を添加し、４時間にわたって重合
を行い、４種のシードポリマーラテックスを得た。これ
らをそれぞれＳ−１〜Ｓ−４とする。Implementation Ml~6. Comparative Examples 1 to 7 (1) Step 11: Synthesis of seed polymer particles Monomers, chain transfer agents, emulsifiers, and ion-exchanged water having the compositions shown in Table 1 were added to an inner volume of 100! The system temperature was further raised to 70°C, and in this state, the polymerization initiator shown in Table 1 was added and polymerization was carried out for 4 hours to obtain four types of seed polymer latex. . These are designated as S-1 to S-4, respectively.
このようにして得られたシードポリマーラテックスの固
形分濃度１重合収率２発生した凝固物の量およびポリマ
ー粒子の数平均粒子径を同じく第１表に示す。Table 1 also shows the solid content concentration, polymerization yield, amount of generated coagulum, and number average particle diameter of the polymer particles of the seed polymer latex thus obtained.
ここにおいて、重合収率は、重合後のミクロゲルの固形
分濃度より求めた。Here, the polymerization yield was determined from the solid content concentration of the microgel after polymerization.
重合安定性は、重合後のミクロゲルを４００メツシユ金
網にてろ過し、金網上に残存した凝固物の量を七ツマ−
に対する割合で示した。Polymerization stability was determined by filtering the microgel after polymerization through a 400-mesh wire mesh, and measuring the amount of coagulated material remaining on the wire mesh by seven microgels.
It is expressed as a percentage of
粒子径については、コールタ−サブミクロン粒子アナラ
イザー（米国、コールタ−φエレクトロニクス社製、
Ｃｏｕｌｔｏｒ Ｍｏｄｅ！ Ｎ４型）で測定した。For particle size, use the Coulter Submicron Particle Analyzer (manufactured by Coulter φ Electronics, USA).
Coulter Mode! N4 type).
（２）第２工程；反応性ミクロゲルの合成第２表に示す
シードポリマーラテックス、モノマー、乳化剤、イオン
交換水を内容量１００！のステンレス製反応器に仕込み
、窒素置換後７０℃に昇温し、さらに過硫酸カリウムを
添加し、５時間にわたって重合を行い、実施例につき６
種、および比較例につき７種の反応性ミクロゲルを得た
。(2) Second step: Synthesis of reactive microgel Seed polymer latex, monomer, emulsifier, and ion-exchanged water shown in Table 2 were added in an amount of 100! The temperature was raised to 70°C after purging with nitrogen, potassium persulfate was added, and polymerization was carried out for 5 hours.
Seven types of reactive microgels were obtained for each species and comparative example.
なお、前記比較例１〜７はいずれもシードポリマーラテ
ックスを用いない場合の例である。It should be noted that all of Comparative Examples 1 to 7 are examples in which no seed polymer latex was used.
ここにおける重合収率、凝固物量、数平均粒子径は、第
１工程で示した方法により求めた。また残留ペンダント
ビニル基についてはフーリエ変換赤外分光装置（ＮＩＣ
ＯＬＥＴ ＪＡＰＡＮ Ｃ０ＲＰＯＲＡＴＩＯＮ。The polymerization yield, amount of coagulated material, and number average particle diameter were determined by the method shown in the first step. For residual pendant vinyl groups, Fourier transform infrared spectroscopy (NIC)
OLET JAPAN CORPORATION.
ｍｏｄｅ ８０ＳＸ）を用い、ＫＢｒ法で行った。mode 80SX) using the KBr method.
具体的には、バラメチルスチレンモノマーを比較とし、
ビニル基およびベンゼン環の吸光度とミクロゲルのそれ
らについての吸光度の関係より、仕込んだ架橋性モノマ
ーのうち何％がペンダントビニル基として残っているか
を定量し、ポリマー固形分１００ｇ当りのミリモル数で
求めた。ただし、このとき、スチレン、アクリル酸など
の非架橋性モノマーは１００％共重合されているものと
して計算した。Specifically, as a comparison of rose methylstyrene monomer,
From the relationship between the absorbance of the vinyl group and benzene ring and the absorbance of the microgel, the percentage of the charged crosslinking monomer remaining as a pendant vinyl group was determined and calculated in millimoles per 100 g of polymer solid content. . However, at this time, the calculation was made assuming that 100% of non-crosslinkable monomers such as styrene and acrylic acid were copolymerized.
第２表に示す結果から明らかなように、比較例１〜６に
おいては、いずれも凝固物量が大きく、安定性が低い。As is clear from the results shown in Table 2, in Comparative Examples 1 to 6, the amount of coagulum was large and the stability was low.
また、比較例２〜６においては、粒子径がきわめて大き
くなり、目的とする粒子径範囲の反応性ミクロゲルを得
ることができなかった。Moreover, in Comparative Examples 2 to 6, the particle size became extremely large, and it was not possible to obtain reactive microgels having the target particle size range.
比較例７のように凝固物量を少なくかつ数平均粒子径を
１０Ｏｎ−より小さくするためには、著しく多量の乳化
剤を必要とした。また粒子径分布も著しく広くなり、ミ
クロゲルとして好ましくなかった。In order to reduce the amount of coagulated material and make the number average particle diameter smaller than 10 On- as in Comparative Example 7, a significantly large amount of emulsifier was required. In addition, the particle size distribution became significantly broad, which was not desirable as a microgel.
これに対し、本発明の実施例１〜６においては、いずれ
も凝固物量が極めて少なく、安定性に優れ、かつ所望の
粒子径範囲を有する反応性ミクロゲルが得られた。On the other hand, in Examples 1 to 6 of the present invention, reactive microgels were obtained in which the amount of coagulated matter was extremely small, excellent in stability, and having a desired particle size range.
［発明の効果］
本発明によれば、粒子径のコントロールを容易に行うこ
とができるだけでなく、乳化剤の濃度を低く抑制した状
態で平均粒子径が１０〜１００ｎｓの範囲の反応性ミク
ロゲルを安定性よくしかも効率的に製造することができ
、さらに架橋性モノマーの系全体に対する使用量も表面
反応性を低下させることなく減することができるので、
低コストで反応性ミクロゲルを製造することができる。[Effects of the Invention] According to the present invention, it is possible not only to easily control the particle size, but also to stabilize reactive microgels with an average particle size in the range of 10 to 100 ns while keeping the emulsifier concentration low. It can be produced easily and efficiently, and the amount of crosslinking monomer used in the entire system can be reduced without reducing surface reactivity.
Reactive microgels can be produced at low cost.
本発明によって得られた反応性ミクロゲルは、粒子表面
に存在する反応性ビニル基を利用することができる分野
あるいは硬度が大きく超微粒子である特性を活用できる
分野等で好適に用いることができ、例えば塗料等のコー
ティング剤、ゴム。The reactive microgel obtained by the present invention can be suitably used in fields where the reactive vinyl groups present on the particle surface can be utilized or where the properties of having large hardness and ultrafine particles can be utilized, for example. Coating agents such as paint, rubber.
樹脂、接着剤２繊維等の添加剤あるいは補強剤、また染
料や医薬、農薬等の固定化用担体などとして有効に使用
することができる。It can be effectively used as an additive or reinforcing agent for resins, adhesive fibers, etc., and as a carrier for immobilizing dyes, medicines, agricultural chemicals, etc.
Claims (1)
とする、数平均粒子径が１０〜１００ｎｍで粒子表面に
ビニル基を有する反応性ミクロゲルの製造方法。 第１工程； ビニル基を２以上有する架橋性モノマーを５．５重量％
以下の割合で含有するビニル系モノマーを乳化重合し、
数平均粒子径が５〜８０ｎｍであるシードポリマー粒子
を合成する工程。 第２工程； 第１工程で得られたシードポリマー粒子５〜１０００重
量部（固形分）の存在下において、ビニル基を２以上有
する架橋性モノマーを６重量％以上含有するビニル系モ
ノマー１００重量部を乳化重合する工程。(1) A method for producing a reactive microgel having a number average particle diameter of 10 to 100 nm and a vinyl group on the particle surface, the method comprising the following first step and second step. 1st step; 5.5% by weight of crosslinkable monomer having 2 or more vinyl groups
Emulsion polymerization of vinyl monomers contained in the following proportions,
A step of synthesizing seed polymer particles having a number average particle diameter of 5 to 80 nm. Second step: In the presence of 5 to 1000 parts by weight (solid content) of the seed polymer particles obtained in the first step, 100 parts by weight of a vinyl monomer containing 6% by weight or more of a crosslinkable monomer having two or more vinyl groups The process of emulsion polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1121867A JP2722661B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing aqueous dispersion of reactive polymer particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1121867A JP2722661B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing aqueous dispersion of reactive polymer particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02300204A true JPH02300204A (en) | 1990-12-12 |
| JP2722661B2 JP2722661B2 (en) | 1998-03-04 |
Family
ID=14821894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1121867A Expired - Lifetime JP2722661B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing aqueous dispersion of reactive polymer particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2722661B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04293907A (en) * | 1991-03-22 | 1992-10-19 | Toyo Ink Mfg Co Ltd | Water-base photoresin composition |
| JP2014512437A (en) * | 2011-04-11 | 2014-05-22 | ヌプレックス レジンズ ビー．ヴィー． | Preparation process of aqueous dispersion of vinyl polymer |
| JP2015507072A (en) * | 2012-02-14 | 2015-03-05 | アクロン ポリマー システムズ，インコーポレイテッド | Process for the preparation of styrenic fluoropolymers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6162510A (en) * | 1984-09-04 | 1986-03-31 | Dainippon Ink & Chem Inc | Preparation of non-film-forming resin emulsion, and its pulverization method |
| JPS6166710A (en) * | 1984-09-11 | 1986-04-05 | Dainippon Ink & Chem Inc | Production of non-film-forming vinyl resin emulsion and method of powdering same |
| JPS61241310A (en) * | 1985-04-18 | 1986-10-27 | Soken Kagaku Kk | Production of emulsion of crosslinked polymer |
-
1989
- 1989-05-15 JP JP1121867A patent/JP2722661B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6162510A (en) * | 1984-09-04 | 1986-03-31 | Dainippon Ink & Chem Inc | Preparation of non-film-forming resin emulsion, and its pulverization method |
| JPS6166710A (en) * | 1984-09-11 | 1986-04-05 | Dainippon Ink & Chem Inc | Production of non-film-forming vinyl resin emulsion and method of powdering same |
| JPS61241310A (en) * | 1985-04-18 | 1986-10-27 | Soken Kagaku Kk | Production of emulsion of crosslinked polymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04293907A (en) * | 1991-03-22 | 1992-10-19 | Toyo Ink Mfg Co Ltd | Water-base photoresin composition |
| JP2014512437A (en) * | 2011-04-11 | 2014-05-22 | ヌプレックス レジンズ ビー．ヴィー． | Preparation process of aqueous dispersion of vinyl polymer |
| JP2015507072A (en) * | 2012-02-14 | 2015-03-05 | アクロン ポリマー システムズ，インコーポレイテッド | Process for the preparation of styrenic fluoropolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2722661B2 (en) | 1998-03-04 |
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