JPH01218629A - Method for producing hollow polymer particles - Google Patents
Method for producing hollow polymer particlesInfo
- Publication number
- JPH01218629A JPH01218629A JP4428288A JP4428288A JPH01218629A JP H01218629 A JPH01218629 A JP H01218629A JP 4428288 A JP4428288 A JP 4428288A JP 4428288 A JP4428288 A JP 4428288A JP H01218629 A JPH01218629 A JP H01218629A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- weight
- particles
- polymer
- parts
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 172
- 229920000642 polymer Polymers 0.000 title claims abstract description 162
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 239000000178 monomer Substances 0.000 claims abstract description 133
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 45
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 17
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000012736 aqueous medium Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 229920006254 polymer film Polymers 0.000 claims abstract description 5
- 239000010419 fine particle Substances 0.000 claims description 82
- 238000006116 polymerization reaction Methods 0.000 claims description 48
- 238000004132 cross linking Methods 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 230000000379 polymerizing effect Effects 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 42
- 239000000126 substance Substances 0.000 description 41
- 239000011148 porous material Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 23
- -1 carboxy modified styrene Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 238000000149 argon plasma sintering Methods 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 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 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 229920003146 methacrylic ester copolymer Polymers 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- JEICNMVISQDKJD-UHFFFAOYSA-N 2-(ethylamino)propyl 2-methylprop-2-enoate Chemical compound CCNC(C)COC(=O)C(C)=C JEICNMVISQDKJD-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 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
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- FYBMJOYJVZCVIZ-UHFFFAOYSA-N 2-(dioctylamino)ethyl 2-methylprop-2-enoate Chemical compound CCCCCCCCN(CCOC(=O)C(C)=C)CCCCCCCC FYBMJOYJVZCVIZ-UHFFFAOYSA-N 0.000 description 1
- OBMRSUNAEQGDLK-UHFFFAOYSA-N 2-(dipropylamino)ethyl 2-methylprop-2-enoate Chemical compound CCCN(CCC)CCOC(=O)C(C)=C OBMRSUNAEQGDLK-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- JWCDUUFOAZFFMX-UHFFFAOYSA-N 2-ethenoxy-n,n-dimethylethanamine Chemical compound CN(C)CCOC=C JWCDUUFOAZFFMX-UHFFFAOYSA-N 0.000 description 1
- CEYHHQSTMVVZQP-UHFFFAOYSA-N 2-ethenoxyethanamine Chemical compound NCCOC=C CEYHHQSTMVVZQP-UHFFFAOYSA-N 0.000 description 1
- RXQKKPDQYISKHD-UHFFFAOYSA-N 2-ethylhexyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCC(CC)COC(=O)C=C RXQKKPDQYISKHD-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
- LEKIODFWYFCUER-UHFFFAOYSA-N 2-methylidenebut-3-enenitrile Chemical compound C=CC(=C)C#N LEKIODFWYFCUER-UHFFFAOYSA-N 0.000 description 1
- JGBOVFKUKBGAJQ-UHFFFAOYSA-N 2-methylidenebutanediamide Chemical compound NC(=O)CC(=C)C(N)=O JGBOVFKUKBGAJQ-UHFFFAOYSA-N 0.000 description 1
- FAVWXKQADKRESO-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-1-ene Chemical compound CC=C.CC(=C)C(O)=O FAVWXKQADKRESO-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DVLDIOYTAAOOML-UHFFFAOYSA-N 4-(diethylamino)butyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCCCOC(=O)C(C)=C DVLDIOYTAAOOML-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NCBWXMZYZBRUQY-UHFFFAOYSA-N CC=C(C(=O)N)CC(=O)N Chemical compound CC=C(C(=O)N)CC(=O)N NCBWXMZYZBRUQY-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 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
- 239000011230 binding agent Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 229940019836 cyclamen aldehyde Drugs 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
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 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
- 235000011180 diphosphates Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- UJKWLAZYSLJTKA-UHFFFAOYSA-N edma Chemical compound O1CCOC2=CC(CC(C)NC)=CC=C21 UJKWLAZYSLJTKA-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 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
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 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
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003204 osmotic effect Effects 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
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- QVKOLZOAOSNSHQ-UHFFFAOYSA-N prop-1-ene;prop-2-enoic acid Chemical compound CC=C.OC(=O)C=C QVKOLZOAOSNSHQ-UHFFFAOYSA-N 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 229940080350 sodium stearate Drugs 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
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
- C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
Description
【発明の詳細な説明】
〈産業」二の利用分野〉
本発明は、中空ポリマー微粒子の製造法に関する。更に
詳しくは、紙、繊維、皮革等のコーティング剤、あるい
は各種の塗料なとに使用しうる光散乱剤あるいは光散乱
助剤又はマイクロカプセルとして有用である内孔を有す
る中空ポリマー微粒子の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industry> Second Field of Application The present invention relates to a method for producing hollow polymer fine particles. More specifically, it relates to a method for producing hollow polymer fine particles having inner pores that are useful as light scattering agents or light scattering aids or microcapsules that can be used as coating agents for paper, fibers, leather, etc., or various paints. It is something.
〈従来の技術〉
粒子内部に孔を有するポリマー粒子はその内孔に各種の
物質を含有させることによりマイクロカプセル粒子とし
て、あるいはその内孔を中空にすることでたとえば光散
乱剤として利用される中空ポリマー粒子などの有機素材
として、利用されている。<Prior art> Polymer particles with pores inside the particles can be used as microcapsule particles by containing various substances in the inner pores, or can be used as microcapsule particles by making the inner pores hollow, which can be used, for example, as light scattering agents. It is used as an organic material such as polymer particles.
従来、内孔を有するポリマー粒子の製造方法としては、
下記の方法が知られている。Conventionally, as a method for producing polymer particles having inner pores,
The following methods are known.
（Ｉ）ポリマー粒子中に発泡剤を含有させ、のちにこの
発泡剤を発泡させる方法。(I) A method in which a foaming agent is contained in polymer particles and the foaming agent is then foamed.
（ＩＩ）ポリマーにブタン等の揮発性物質を封入し、の
ちにこの揮発性物質をガス化膨潤させる方法。(II) A method in which a volatile substance such as butane is encapsulated in a polymer, and the volatile substance is then gasified and swollen.
（Ｉ［［）ポリマーを溶融させ、これに空気等の気体ジ
ェットを吹付け、気泡を封入する方法。(I [[) A method in which a polymer is melted and a jet of gas such as air is blown thereto to seal in air bubbles.
（ＩＶ）ポリマー粒子の内部にアルカリ膨潤性の物質を
浸透させて、アルカリ膨潤性の物質を膨潤させる方法。(IV) A method of infiltrating an alkali-swellable substance into the interior of polymer particles to swell the alkali-swellable substance.
（■）ｗ１０／Ｗ型モノマーエマルジョンヲｆ１４−４
＝
し、重合を行なう方法。(■) w10/W type monomer emulsion wo f14-4
= method of polymerization.
（Ｖｌ）不飽和ポリエステル溶液中に顔料を懸濁させた
懸濁溶液中でモノマーを重合する方法。(Vl) A method of polymerizing monomers in a suspension solution in which a pigment is suspended in an unsaturated polyester solution.
（■）架橋ポリマー粒子をシードとして、相溶性の異な
るポリマーをそのシード上に重合、架橋する二段階架橋
方法。(■) A two-step crosslinking method in which crosslinked polymer particles are used as seeds and polymers with different compatibility are polymerized and crosslinked onto the seeds.
（■）ポリマーの重合収縮により製造する方法。(■) A method of manufacturing by polymerization shrinkage of a polymer.
〈発明が解決しようとする問題点〉
しかし、これらの製造方法では、製造条件のコントロー
ルあるいは、所望の内孔を有するポリマー粒子を安定に
製造することか難かしかった。又、従来の中空微粒子は
、塗膜形成物質に光散乱剤として添加した場合に、要求
される物性である隠ぺい性を有したが、光沢、塗膜強度
、弾性、接着性、耐水性、耐アルカリ性、耐候性等の物
性バランスが劣っていた。特に従来の内孔を有するポリ
マー粒子の製造方法では、ポリマー粒子中に内孔を発現
さぜるために、シェルのポリマーとしてガラス転移温度
の高いものを使用することが必要となるか、それによっ
て接着性の良好な内孔を有するポリマー粒子が得られな
いという致命的な問題点を有していた。<Problems to be Solved by the Invention> However, in these production methods, it is difficult to control production conditions or to stably produce polymer particles having desired internal pores. In addition, conventional hollow fine particles had the required physical properties of hiding when added as a light-scattering agent to a coating film-forming substance, but they had poor gloss, coating strength, elasticity, adhesion, water resistance, and resistance. The balance of physical properties such as alkalinity and weather resistance was poor. In particular, in conventional methods for producing polymer particles with internal pores, in order to develop internal pores in the polymer particles, it is necessary to use a polymer with a high glass transition temperature as the shell polymer, or This method had a fatal problem in that polymer particles having inner pores with good adhesiveness could not be obtained.
本発明は、このような従来技術の問題点を解決した中空
微粒子とその製造方法を提供するものである。The present invention provides hollow fine particles that solve the problems of the prior art and a method for producing the same.
〈問題を解決するための手段〉
本発明は
（Ａ） 平均粒径が０．０５〜１５μｍの範囲にある
第１の中空ポリマー微粒子、および
（Ｂ） 重合性不飽和カルボン酸０〜８０重量％と他
の共重合可能なモノマー２０〜１００重量％からなるモ
ノマー又はモノマー混合物を
（Ｃ） 上記第１の中空ポリマー微粒子（Ａ）とモノ
マー又はモノマー混合物（Ｂ）の合計重量１００重量部
当り５重量以下の乳化剤及び／又は分散剤
の存在下、水性媒体中で重合に付し、該第１の中空ポリ
マー微粒子（Ａ）の表面に該モノマー又はモノマー混合
物（Ｂ）の重合体被膜を生成せしめて平均粒径が０．１
〜２０μｍの範囲にある第２の中空ポリマー微粒子を形
成することを特徴とする中空ポリマー微粒子の製造法を
提供するものである。<Means for solving the problem> The present invention comprises (A) first hollow polymer fine particles having an average particle size in the range of 0.05 to 15 μm, and (B) 0 to 80% by weight of a polymerizable unsaturated carboxylic acid. and other copolymerizable monomer (C) 5 parts by weight per 100 parts by weight of the total weight of the first hollow polymer fine particles (A) and the monomer or monomer mixture (B). Polymerization is performed in an aqueous medium in the presence of the following emulsifier and/or dispersant to form a polymer film of the monomer or monomer mixture (B) on the surface of the first hollow polymer fine particles (A). Average particle size is 0.1
The present invention provides a method for producing hollow polymer fine particles characterized by forming second hollow polymer fine particles having a diameter in the range of ~20 μm.
以下本発明について詳細に説明する。The present invention will be explained in detail below.
（Ｉ）本発明の（Ａ）成分である平均粒子径が０゜０５
〜１５μｍの範囲にある第１の中空ポリマー微粒子につ
いて：
（Ａ）成分の中空微粒子は従来の技術の項で示した（Ｉ
）〜（■）の方法及びその他の方法により製造すること
ができる。(I) The average particle diameter of component (A) of the present invention is 0°05
Regarding the first hollow polymer fine particles in the range of ~15 μm: The hollow fine particles of component (A) are as described in the prior art section (I
) to (■) and other methods.
第１の中空微粒子（Ａ）の平均粒子径は０．０５〜１５
μｍ１好ましくは０．１５〜ｌＯμｍである。The average particle diameter of the first hollow fine particles (A) is 0.05 to 15
μm1 is preferably 0.15 to 10 μm.
平均粒子径が０．０５μｍ未満であると製造しにくく、
又製造できたとしても、中空を有さないポリマー粒子が
少くとも一部生成され、それらが含有されるので好まし
くない。一方、外径が１５μｍを超えると粒子径分布が
ブロードになり、これを第１の中空微粒子（Ａ）として
用いて得られる第２の中空微粒子は粒子径のそろったも
のとして得られず好ましくない。If the average particle diameter is less than 0.05 μm, it is difficult to manufacture;
Even if it can be produced, it is not preferable because at least some polymer particles without hollow spaces are produced and contained. On the other hand, if the outer diameter exceeds 15 μm, the particle size distribution becomes broad, and the second hollow particles obtained by using these as the first hollow particles (A) cannot be obtained with uniform particle sizes, which is not preferable. .
第１の中空微粒子（Ａ）の外径に対する内径の比は好ま
しくは０．１５〜０．９倍である。０．１５倍以上であ
ると１段と優れた本発明の目的とする物性の中空微粒子
が得られるので好ましく、一方０．９倍を超えると、第
１の中空微粒子（Ａ）の製造が困難になり、工業的生産
としては、好ましくない。The ratio of the inner diameter to the outer diameter of the first hollow fine particles (A) is preferably 0.15 to 0.9 times. If it is 0.15 times or more, it is preferable because hollow fine particles with even better physical properties, which are the object of the present invention, can be obtained.On the other hand, if it exceeds 0.9 times, it is difficult to produce the first hollow fine particles (A). This is not desirable for industrial production.
第１の中空微粒子（Ａ）の好ましい製造方法は、特開昭
６１〜６２５１０号及び特開昭６１〜６６７１０号等で
提案されている従来の技術項で示した（■）の方法及び
特開昭６１〜８７７３４号、特開昭６１〜８６９４１号
、特開昭６２−１２７３３６号、特開昭６２−１５６３
８７号等で提案されている従来の技術項で示した（■）
の方法である。これらの方法の第１の中空微粒子（Ａ）
を用いて得られた第２の、中空微粒子は隠ぺい性に優れ
る。特に好ましくは（■）の方法であり、この方法では
中空微粒子の外径、内径のコントロールが容易であり、
その結果、得られた中空微粒子を第１の中空微粒子（Ａ
）として用いて得られた第２の中空微粒子は隠ぺい性、
耐溶剤性、耐熱性に優れている。Preferred methods for producing the first hollow fine particles (A) include the method (■) shown in the conventional technical section proposed in JP-A-61-62510 and JP-A-61-66710, etc.; 1986-87734, JP-A-61-86941, JP-A-62-127336, JP-A-62-1563
As shown in the conventional technical section proposed in No. 87 etc. (■)
This is the method. First hollow fine particles (A) of these methods
The second hollow fine particles obtained using the method have excellent hiding properties. Particularly preferred is the method (■), which allows easy control of the outer diameter and inner diameter of the hollow particles,
As a result, the obtained hollow fine particles were transformed into first hollow fine particles (A
) The second hollow fine particles obtained using
Excellent solvent resistance and heat resistance.
（■）の方法の中で最も優。れているのは特開昭６２−
１２７３３６号の方法で得られる第１の中空微粒子（Ａ
）であり、この方法は、第１の中空微粒子（Ａ）の重合
に於ける重合安定性及び生産性に於いて優れており、又
、物性上は隠ぺい性が優れている。(■) is the best of the methods. The one shown is Japanese Patent Application Publication No. 1986-
The first hollow fine particles (A
), and this method is excellent in polymerization stability and productivity in the polymerization of the first hollow fine particles (A), and also has excellent hiding properties in terms of physical properties.
第１の中空微粒子（Ａ）の好ましい構成組成について以
下に示す。The preferred composition of the first hollow fine particles (A) is shown below.
第１の中空ポリマー微粒子（Ａ）としては該ポリマーか
（ａ）親水性の非架橋性モノマー２０〜９９重量％、架
橋性モノマー１〜８０重量％及びこれらのモノマーと共
重合可能な他のモノマー０〜７０重量％からなるモノマ
ー成分の共重合体、および
（ｂ）上記共重合体とは異なる重合体、から成り、そし
て
（ｃ）上記重合体（ａ）１００重量部に対し、上記重合
体（ｂ）１〜１００重量部の組成、を有するものが好ま
しい。更に好ましくは（ａ）成分が非架橋性モノマー４
０〜９８重量％、架橋性モノマー２〜６０重量％、およ
びこれらと共重合可能な他のモノマー０〜７０重量％で
ある。The first hollow polymer fine particles (A) include the polymer (a) 20 to 99% by weight of a hydrophilic non-crosslinking monomer, 1 to 80% by weight of a crosslinking monomer, and other monomers copolymerizable with these monomers. (b) a polymer different from the above copolymer, and (c) the above polymer based on 100 parts by weight of the above polymer (a); (b) A composition having a composition of 1 to 100 parts by weight is preferred. More preferably, component (a) is a non-crosslinking monomer 4.
0 to 98% by weight, 2 to 60% by weight of the crosslinking monomer, and 0 to 70% by weight of other monomers copolymerizable with these.
（ａ）成分中の親水性の非架橋性モノマーの種類につい
ては、特に限定するものでないが、好ましくは不飽和カ
ルボン酸及び／又はそれ以外の親水性モノマーとからな
る。The type of hydrophilic non-crosslinkable monomer in component (a) is not particularly limited, but it preferably consists of an unsaturated carboxylic acid and/or other hydrophilic monomer.
（ａ）成分中の親水性の非架橋性モノマーの種類として
、更に好ましくは不飽和カルボン酸および／またはそれ
以外の親木性モノマーからなり、特に好ましくは、その
組成割合は不飽和カルボン酸１〜７０重量％とそれ以外
の親水性モノマー３０〜９９からなるものである。The type of hydrophilic non-crosslinking monomer in component (a) is more preferably unsaturated carboxylic acid and/or other wood-philic monomer, particularly preferably the composition ratio is 1 unsaturated carboxylic acid 1 ~70% by weight and 30~99% of other hydrophilic monomers.
第１の中空微粒子（Ａ）の（ａ）成分として上記の好ま
しい、更に好ましいと示したものを使用することて、１
段と優れた本発明の目的とする物性の中空微粒子を製造
することができる。By using the above-mentioned preferred and more preferred components as the component (a) of the first hollow fine particles (A), 1
Hollow fine particles having much better physical properties as the object of the present invention can be produced.
第１の中空微粒子（Ａ）の上記（ｌ〕）成分である重合
体（以下異種ポリマーという）は（ａ）成分で示された
モノマーから得られる共重合体とは異なるものであり、
かつ重合性モノマーに溶解もしくは膨潤しやすいもので
あることが必要である。The polymer (hereinafter referred to as a heterogeneous polymer) that is the component (l) of the first hollow fine particles (A) is different from the copolymer obtained from the monomer shown as the component (a),
In addition, it needs to be easily soluble or swollen in the polymerizable monomer.
このような異種ポリマーとしては、具体的には、ポリス
チレン、カルボキシ変性ポリスチレン、カルボキシ変性
スチレンブタジェンコポリマー、スチレンブタジェンコ
ポリマー、スチレンアクリルエステルコポリマー、スチ
レンメタクリルエステルコポリマー、アクリルエステル
コポリマー、メタクリルエステルコポリマー、カルボキ
シ変性スチレンアクリルエステルコポリマー、カルボキ
シ変性スチレンアクリルエステルコポリマー、カルボキ
シ変性アクリルエステルコポリマー、カルボキシ変性メ
タクリルエステルコポリマーなとか例示される。Specifically, such different polymers include polystyrene, carboxy-modified polystyrene, carboxy-modified styrene-butadiene copolymer, styrene-butadiene copolymer, styrene-acrylic ester copolymer, styrene-methacrylic ester copolymer, acrylic ester copolymer, methacrylic ester copolymer, carboxy Examples include modified styrene acrylic ester copolymer, carboxy modified styrene acrylic ester copolymer, carboxy modified acrylic ester copolymer, and carboxy modified methacrylic ester copolymer.
これらのうち特にポリスチレン又はスチレン成分を５０
重量％以上含むスチレンコポリマーが好ましい。Among these, polystyrene or styrene components are particularly
Styrene copolymers containing at least % by weight are preferred.
第１の中空微粒子（Ａ）の（ｂ）成分である上記−１１
〜
異種ポリマーの量は、（ａ）成分の共重合体１００重量
部に対し、１〜ｌＯＯ重量部、好ましくは２〜５０重量
部、更に好ましくは５〜２０重量部である。-11 above, which is the (b) component of the first hollow fine particles (A)
~ The amount of the different polymer is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the copolymer of component (a).
第１の中空微粒子（Ａ）は、上記のとおり、好ましくは
、
（ａ）親水性の非架橋性モノマー２０〜９９重量％、架
橋性モノマー１〜８０重量％およびこれらのモノマーと
共重合可能な他の七ツマー０〜７０重量％からなるモノ
マー成分を、
（ｂ）上記モノマー成分から得られる共重合体と異なる
種となるポリマー微粒子、
の存在下、該モノマー成分１００重量部当り該ポリマー
微粒子１〜１００重量部の割合で存在せしめて、水性媒
体中で重合に付して平均粒径が０゜０５〜１５μｍの範
囲にある第１の中空ポリマー微粒子を形成せしめること
によって製造される。As described above, the first hollow fine particles (A) preferably contain (a) 20 to 99% by weight of a hydrophilic non-crosslinkable monomer, 1 to 80% by weight of a crosslinkable monomer, and copolymerizable with these monomers. A monomer component consisting of 0 to 70% by weight of other heptamers is added in the presence of (b) polymer fine particles that are a different species from the copolymer obtained from the monomer component, 1 of the polymer fine particles per 100 parts by weight of the monomer component. -100 parts by weight, and polymerize in an aqueous medium to form first hollow polymer fine particles having an average particle size in the range of 0.05 to 15 .mu.m.
その際上記（ｂ）成分の異種ポリマーの使用量は、（ａ
）成分のモノマー１００重量部に対して、好ましくは２
〜５０重量部、更に好ましくは５〜２０重量部である。In this case, the amount of the dissimilar polymer used as component (b) is (a
) Preferably 2 parts by weight of monomer of component
~50 parts by weight, more preferably 5 to 20 parts by weight.
上記いずれの方法においても、異種ポリマーの使用量が
１重量部未満であると内孔を形成する効果が小さく、異
種ポリマーが１００重量部を超えるとかえって、内孔の
形成が抑制される傾向を示すので好ましくない。In any of the above methods, if the amount of different polymer used is less than 1 part by weight, the effect of forming inner pores is small, and if the amount of different polymer used exceeds 100 parts by weight, the formation of inner pores tends to be suppressed. This is not desirable because it shows
また、上記（ａ）成分の親水性の非架橋性モノマーとし
ては例えはビニルピリジン、グリンジルアクリレート、
グリンジルメタクリレート、メチルアクリレート、メチ
ルメタクリレート、アクリロニトリル、アクリルアミド
、メタクリルアミド、Ｎ−メチロールアクリルアミド、
Ｎ−メチロールメタクリルアミド、アクリル酸、メタク
リル酸、イタコン酸、フマル酸、スチレンスルホン酸ナ
トリウム、酢酸ビニル、シメチルアミノエヂルメタクリ
レ−１・、ジエチルアミノエチルメタクリレ−［・、２
−ヒドロキシエチルメタクリレート、２−ヒドロキンプ
ロビルメタクリレ−１・なとのビニル系モノマーを例示
することができる。In addition, examples of the hydrophilic non-crosslinkable monomer of component (a) include vinylpyridine, grindyl acrylate,
Grindyl methacrylate, methyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, methacrylamide, N-methylolacrylamide,
N-methylolmethacrylamide, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, sodium styrene sulfonate, vinyl acetate, dimethylaminoedyl methacrylate-1, diethylaminoethyl methacrylate-[, 2]
Examples include vinyl monomers such as -hydroxyethyl methacrylate and 2-hydroquineprobyl methacrylate-1.
これらのうち、好ましく使用されるものはメタクリル酸
などの不飽和カルボン酸、メチルメタクリレート、ビニ
ルピリジン、２−ヒドロキシエチルメタクリレート、な
どである。これらの親水性の非架橋性モノマーは水に対
する溶解度が０．５重量％以上特に１重量％以上である
ことが好ましい。Among these, those preferably used are unsaturated carboxylic acids such as methacrylic acid, methyl methacrylate, vinyl pyridine, 2-hydroxyethyl methacrylate, and the like. These hydrophilic non-crosslinking monomers preferably have a solubility in water of 0.5% by weight or more, particularly 1% by weight or more.
また、上記（ａ）成分の架橋性モノマーとしては、例え
ばジビニルベンゼン、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
リメチロールプロパントリメタクリレート、アリルメタ
クリレートなどのジビニル第七ツマ−あるいはトリビニ
ル系モノマー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およびトリ
メチロールプロパントリメタクリレートが好ましい。Examples of the crosslinking monomer of component (a) include divinyl seventh monomers or trivinyl monomers such as divinylbenzene, ethylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. Among them, divinylbenzene, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate are particularly preferred.
さらに、上記（ａ）成分の共重合可能な他のモノマーと
してはラジカル重合性を有するものであれば特に制限さ
れず、例えばスチレン、ａ−メチルスチレン、ｐ−メチ
ルスチレン、ハロゲン化スチレンの如き芳香族ビニル単
量体、プロピオン酸ビニルの如きビニルエステル類、エ
チルメタクリレート、ブチルアクリレート、ブチルメタ
クリレート、２−エチルへキシルアクリレート、２−エ
チルへキシルメタクリレート、ラウリルアクリレート、
ラウリルメタクリレートの如き、エチレン性不飽和カル
ボン酸アルキルエステル、ブタジェン、イソプレンの如
き共役ジオレフィンなどを例示することができ、特にス
チレン及びエチレン性不飽和カルボン酸アルキルエステ
ルが好ましい。Further, the other copolymerizable monomers of component (a) are not particularly limited as long as they have radical polymerizability, such as aromatic styrene, a-methylstyrene, p-methylstyrene, and halogenated styrene. group vinyl monomers, vinyl esters such as vinyl propionate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate,
Examples include ethylenically unsaturated carboxylic acid alkyl esters such as lauryl methacrylate, conjugated diolefins such as butadiene and isoprene, and styrene and ethylenically unsaturated carboxylic acid alkyl esters are particularly preferred.
（ａ）成分に於ける各七ツマ−の更に好ましい組成割合
は親水性の非架橋性モノマー４０〜９８重量％、架橋性
モノマー２〜６０重量％、および他の共重合可能なモノ
マー０〜７０重量％である。A more preferable composition ratio of each of the seven monomers in component (a) is 40 to 98% by weight of the hydrophilic non-crosslinkable monomer, 2 to 60% by weight of the crosslinkable monomer, and 0 to 70% by weight of the other copolymerizable monomer. Weight%.
親木性モノマーの使用量が過小であると、異種ポリマー
の相分離が不十分であったり、あるいは異種ポリマーが
ポリマー粒子の表面に露出するなどして、内孔の形成が
不確実となる傾向を示すので好ましくない。架橋性モノ
マーの使用量が過小であると、重合中の粒子の強度が不
十分となって粒子全体が収縮してしまい、粒子内部の重
合収縮による歪が不足して内孔が形成されなくなったり
、あるいは内孔を有するポリマー粒子が形成されたとし
ても殻の強度が小さくなるなどの問題を生ずる。If the amount of wood-philic monomer used is too small, the phase separation of different types of polymers may be insufficient, or different types of polymers may be exposed on the surface of the polymer particles, resulting in uncertain formation of inner pores. This is not desirable because it indicates If the amount of crosslinking monomer used is too small, the strength of the particles during polymerization will be insufficient and the entire particle will shrink, and the internal pores may not be formed due to insufficient strain due to polymerization contraction inside the particle. Alternatively, even if polymer particles with internal holes are formed, problems such as a decrease in the strength of the shell occur.
一方、架橋性モノマーの使用量が過大であると、異種ポ
リマーが、重合中に生成するポリマー粒子の外側に排斥
される傾向が生じ、その結果得られるポリマー粒子が真
球状とならず、凹凸のある塊状粒子となる問題を生ずる
。On the other hand, if the amount of crosslinking monomer used is too large, different types of polymers tend to be excluded to the outside of the polymer particles formed during polymerization, and as a result, the resulting polymer particles are not perfectly spherical and have irregularities. This results in some lumpy particle problems.
第１の中空微粒子（Ａ）の製造方法は、特開昭６２−１
２７３３６号の重合技術を用いて、上記したとおり（ｂ
）成分の異種ポリマーの存在下に（ａ）成分のモノマー
を重合することにより得られる。The method for manufacturing the first hollow fine particles (A) is disclosed in JP-A-62-1
27336, as described above (b
It is obtained by polymerizing the monomer of component (a) in the presence of a different polymer of component (a).
上記製造方法は、（ｂ）成分の異種ポリマーとして微粒
子を用い、この微粒子（種ポリマー粒子）に（ａ）成分
のモノマー成分と必要に応じて油性物質とを吸収させ、
その後上記モノマー成分を重合させる（イ）の方法ある
いは、（ｂ）成分の異種ポリマーを（ａ）成分のモノマ
ー成分と必要に応じて油性物質とに溶解させて油性溶液
を形成し、この油性溶液を水に微分散して水中油滴型エ
マルジョンを生成し、その後上記モノマー成分を重合さ
せる（口）の方法によって、実施できる。上記に於いて
異種ポリマーとともに油性物質を存在させることにより
、ポリマー粒子の内孔の径をコントロールすることが容
易になる。The above manufacturing method uses fine particles as the heterogeneous polymer of the component (b), and allows the fine particles (seed polymer particles) to absorb the monomer component of the component (a) and an oily substance as necessary,
Thereafter, the above-mentioned monomer components are polymerized by the method (a), or the dissimilar polymer of component (b) is dissolved in the monomer component of component (a) and an oily substance as necessary to form an oily solution, and this oily solution is It can be carried out by the method of finely dispersing in water to form an oil-in-water emulsion, and then polymerizing the monomer components. In the above, the presence of an oily substance together with a different type of polymer makes it easy to control the diameter of the inner pores of the polymer particles.
異種ポリマーを上記（イ）の方法によって粒子状態で用
いる場合には、これが種（シード）ポリマー粒子として
機能し、これに重合性モノマーおよび油性物質が吸収さ
れることから、当該異種ポリマーは重合性モノマーおよ
び油性物質の吸収性が良好であることが好ましい。その
ためには、異種ポリマーは分子量が小さいものであるこ
とが好ましく、たとえば、その数平均分子量が２０，０
００以下、好ましくは１０，０００以下、さらに好まし
くは７００〜７，０００である。なお、ここにおける数
平均分子量は、異種ポリマーをその良溶媒に溶かし、得
られた溶液をゲルパーミエージョンクロマトグラフィー
（Ｇ Ｐ Ｃ）、浸透圧分子量測定装置、蒸気圧低下性
分子量測定装置などの通常の方法で測定して得られるも
のである。When a foreign polymer is used in the form of particles by the method (a) above, the foreign polymer functions as a seed polymer particle and absorbs the polymerizable monomer and oily substance, so the foreign polymer is polymerizable. It is preferable that the absorbency of monomers and oily substances is good. For this purpose, it is preferable that the different polymer has a small molecular weight, for example, the number average molecular weight is 20.0.
00 or less, preferably 10,000 or less, more preferably 700 to 7,000. Note that the number average molecular weight here refers to dissolving a different type of polymer in its good solvent and measuring the resulting solution using gel permeation chromatography (GPC), an osmotic pressure molecular weight measuring device, a vapor pressure lowering molecular weight measuring device, etc. It can be obtained by measuring using a normal method.
異種ポリマーの数平均分子量か２０，０００より大きい
と、種ポリマー粒子に吸収されないモノマーが多くなり
、これか水性分散体中において種ポリマー粒子と別個に
重合し、その結果内孔を有するポリマー粒子とならない
微粒子が多量に生成するだけでなく、重合系が不安定と
なる問題が生ずる。If the number average molecular weight of the foreign polymer is greater than 20,000, more monomer will not be absorbed into the seed polymer particles and will polymerize separately with the seed polymer particles in the aqueous dispersion, resulting in polymer particles with internal pores. In addition to producing a large amount of undesirable fine particles, the problem arises that the polymerization system becomes unstable.
また、種ポリマー粒子として用いられる異種ポリマーの
粒子径は、目的とする内孔を有するポリマー粒子の外径
の０．３〜０．８倍であることが好ましい。Further, the particle diameter of the different polymer used as the seed polymer particles is preferably 0.3 to 0.8 times the outer diameter of the polymer particles having the intended inner pores.
このような種ポリマー粒子として用いられる異種ポリマ
ーを製造する方法は特に制限されないが、たとえは連鎖
移動剤を比較的多量に使用した乳化重合あるいは懸濁重
合などの製造方法を用いることができる。There are no particular restrictions on the method for producing the dissimilar polymer used as such seed polymer particles, but for example, emulsion polymerization or suspension polymerization using a relatively large amount of a chain transfer agent can be used.
なお、異種ポリマーを種ポリマー粒子として用いる場合
には、この種ポリマー粒子にあらかしめ水に対する溶解
度が１０−３重量％以下の高親油性物質を吸収させてお
くことにより、種ポリマー粒子に対する重合性モノマー
および油性物質の吸収能力を増大することかできる。When using a different type of polymer as the seed polymer particles, the polymerizability of the seed polymer particles can be increased by absorbing a highly lipophilic substance having a solubility in water of 10-3% by weight or less into the seed polymer particles. The absorption capacity of monomers and oily substances can be increased.
このように種ポリマー粒子に高親油性物質を吸収させる
手段を用いる場合には、異種ポリマーの数平均分子量は
２０，０００を超えてもよい。When such a means of absorbing a highly lipophilic substance into the seed polymer particles is used, the number average molecular weight of the different polymer may exceed 20,000.
上記高親油性物質としては、■−クロルドデカン、オク
タノイルペルオキシド、３，５，５−トリメチルヘキサ
ノイルペルオキシドなどを例示することができる。Examples of the highly lipophilic substance include -chlordodecane, octanoyl peroxide, and 3,5,5-trimethylhexanoyl peroxide.
これらの高親油性の物質を種ポリマー粒子に吸収させる
には、当該高親油性物質を微分散させた水性分散体を調
製し、この分散体と種ポリマー粒子の水性分散体とを混
合して前記高親油性物質と種ポリマー粒子とを接触させ
るとよい。In order to absorb these highly lipophilic substances into the seed polymer particles, an aqueous dispersion in which the highly lipophilic substances are finely dispersed is prepared, and this dispersion is mixed with an aqueous dispersion of the seed polymer particles. It is preferable to bring the highly lipophilic substance into contact with the seed polymer particles.
種ポリマー粒子を用いた場合に得られる内孔を有するポ
リマー粒子の粒子径は、種ポリマー粒子か重合性七ツマ
−および油性物質を吸収して肥大化した粒子の粒子径と
おおよそ一致する。このため、種ポリマー粒子の粒子径
、重合性モノマーおよび油性物質に対する種ポリマー粒
子の相対的使用量などを調整することにより、生成する
内孔を有するポリマー粒子の粒子径をコントロールする
ことができる。When seed polymer particles are used, the particle size of the polymer particles having internal pores roughly corresponds to the particle size of the particles enlarged by the seed polymer particles absorbing the polymerizable hexamer and the oily substance. Therefore, by adjusting the particle size of the seed polymer particles, the relative amount of the seed polymer particles used relative to the polymerizable monomer and the oily substance, etc., the particle size of the produced polymer particles having internal pores can be controlled.
具体的には、内孔を有するポリマー粒子の製造において
、白色度および隠ペイカの優れた０、１〜０．６μｍの
粒子径の中空ポリマー粒子を得るためには、種ポリマー
粒子として０．０６〜０．４０μｍの粒子径のものを用
いればよい。Specifically, in the production of polymer particles having internal pores, in order to obtain hollow polymer particles with a particle diameter of 0.1 to 0.6 μm that have excellent whiteness and hidden space, 0.06 μm as a seed polymer particle is required. It is sufficient to use particles having a particle size of ~0.40 μm.
また、種ポリマー粒子を用いることは、粒子径が１μｍ
以下の小粒径の内孔を有するポリマー粒子を製造する湯
釜に、小粒径のモノマー液滴を容易にそして安定に形成
できる点で特に好ましい。In addition, using seed polymer particles means that the particle size is 1 μm.
It is particularly preferable in that monomer droplets of small particle size can be easily and stably formed in a kettle for producing polymer particles having internal pores of the following small particle size.
異種ポリマーを前記（ロ）の方法で使用する場合には、
異種ポリマーの分子量は特に制限されず、数平均分子量
が２０，０００以上のものを好ましく使用することがで
きる。When using a different type of polymer in the method (b) above,
The molecular weight of the different polymer is not particularly limited, and those having a number average molecular weight of 20,000 or more can be preferably used.
この製造方法においては、必要に応して油性物質を用い
ることができる。かかる油性物質としては、水に対する
溶解度が０．２重量％以下の親油性のものであれば特に
制限されず、植物油、動物油、鉱物油、合成油いずれも
使用することができる。In this production method, an oily substance can be used if necessary. Such oily substances are not particularly limited as long as they are lipophilic and have a solubility in water of 0.2% by weight or less, and any of vegetable oils, animal oils, mineral oils, and synthetic oils can be used.
この製造方法においては、油性物質を用いなくとも内孔
を有するポリマー粒子を得ることができるが、油性物質
を用いそしてその使用量などを調節することにより内孔
の径を確実にコントロールすることができる。In this production method, polymer particles with inner pores can be obtained without using an oily substance, but the diameter of the inner pores can be reliably controlled by using an oily substance and adjusting the amount used. can.
前記油性物質としては、例えばラード油、オリーブ油、
ヤシ油、ヒマシ油、綿実油、灯油、ベンゼン、トルエン
、キシレン、ブタン、ペンタン、ヘキサン、シクロヘキ
サン、二硫化炭素、四塩化炭素なとを例示することかで
きる。Examples of the oily substance include lard oil, olive oil,
Examples include coconut oil, castor oil, cottonseed oil, kerosene, benzene, toluene, xylene, butane, pentane, hexane, cyclohexane, carbon disulfide, and carbon tetrachloride.
また、油性物質としては、さらにオイゲノール、ゲラニ
オール、シクラメンアルデヒド、シトロネラール、ジオ
クチルフタレ−１〜、ジブチルフタレートなとの高沸点
油も用いることができる。これら４の高沸点油を用いる
と、コア中に香料、可塑剤などが含まれたカプセル状ポ
リマー粒子が得られる。Further, as the oily substance, high boiling point oils such as eugenol, geraniol, cyclamenaldehyde, citronellal, dioctyl phthalate-1 to dibutyl phthalate can also be used. When these 4 high boiling point oils are used, capsule-like polymer particles containing perfume, plasticizer, etc. in the core can be obtained.
油性物質の使用量は、通常、モノマー全成分１００重量
部に対して０〜ｉ 、ｏ ｏ ｏ重量部、好ましくは０
〜３００重量部である。なお、架橋性モノマー材料とし
て供給されるもののなかに通常含有される不活性溶剤類
も、ここにおける油性物質として算入することができる
。上記油性物質の使用量が過大であると相対的にモノマ
ー成分が不足してポリマーの外殻の膜厚が薄くなり、カ
プセルの強度が不十分となって圧潰されやすいという問
題を生ずる。The amount of the oily substance used is usually 0 to i, o o o parts by weight, preferably 0, based on 100 parts by weight of all monomer components.
~300 parts by weight. Incidentally, inert solvents normally contained in those supplied as crosslinkable monomer materials can also be included as oily substances here. If the amount of the oily substance used is too large, the monomer component will be relatively insufficient and the thickness of the outer shell of the polymer will become thin, causing the problem that the strength of the capsule will be insufficient and it will be easily crushed.
また、前記油性物質の概念には、既に述べた重合性モノ
マーを含むことができる。この場合には、重合工程にお
いて、生成するポリマー粒子の内部に重合性モノマーが
残った状態で重合を停止させることにより、この残余の
モノマーを油性物質として代用することができる。この
場合、重合収率は９７％以下、好ましくは９５％以下に
留′める必要がある。このためには、少量の重合抑制剤
を加えて重合する方法、重合途中で反応系の温度を下げ
る方法、あるいは重合途中で重合停止剤を加えて重合を
停止させる方法などを採用することができる。Furthermore, the concept of the oily substance can include the already mentioned polymerizable monomers. In this case, in the polymerization step, by stopping the polymerization with the polymerizable monomer remaining inside the produced polymer particles, this remaining monomer can be used as an oily substance. In this case, the polymerization yield must be kept at 97% or less, preferably 95% or less. For this purpose, methods such as adding a small amount of polymerization inhibitor to polymerize, lowering the temperature of the reaction system during polymerization, or adding a polymerization terminator during polymerization to stop polymerization can be adopted. .
また、この製造方法においては、油性物質を含むカプセ
ル状ポリマー粒子あるいは上述のように油性物質を水と
置換して得られる含水中空ポリマー粒子を水性分散体よ
り分離して乾燥処理することにより、内部に空間を有す
る中空ポリマー粒子が得られる。In addition, in this production method, the capsule-like polymer particles containing an oily substance or the hollow polymer particles containing water obtained by replacing the oily substance with water as described above are separated from the aqueous dispersion and subjected to a drying treatment, whereby the internal Hollow polymer particles having spaces are obtained.
上記した重合技術を用いて得られる（Ａ）成分の中空微
粒子は次の長所を有している。The hollow fine particles of component (A) obtained using the above polymerization technique have the following advantages.
（ｉ）！＆造工程が簡単でありかつ生産性に優れる。(i)! & The manufacturing process is simple and has excellent productivity.
（■）製造コントロールが容易であり、目的とする外径
、内径の中空微粒子が得られる。(■) Production control is easy, and hollow particles with the desired outer diameter and inner diameter can be obtained.
（ｉｉｉ）中空微粒子の水性分散体のｐＨは自由に選択
できるので該中空微粒子の表面に形成させる重合体の七
ツマ−に制限なく使用できる。(iii) Since the pH of the aqueous dispersion of hollow fine particles can be freely selected, it can be used without any restriction in terms of the amount of polymer to be formed on the surface of the hollow fine particles.
（１ｖ）この中空微粒子を本発明の第１の中空微粒＝２
３−
子（Ａ）として用いて、得られた第２の中空微粒子は一
段と優れた隠ぺい性、光沢、接着性、塗膜、強度を示す
。(1v) This hollow fine particle is the first hollow fine particle of the present invention = 2
3- When used as the child (A), the obtained second hollow fine particles exhibit even better hiding properties, gloss, adhesion, coating film, and strength.
本発明の（Ｂ）成分について：
（Ｂ）成分の重合性の不飽和カルボン酸としては、例え
ばアクリル酸、メタクリル酸、クロトン酸、マレイン酸
、７マール酸、イタコン酸等のモノまたはジカルボン酸
、ジカルボン酸の酸無水物、ジカルボン酸のモノアルキ
ルエステル、ジカルボン酸のモノアミド等を好ましいも
のとして挙げられる。この中でより好ましくはアクリル
酸、メタクリル酸およびイタコン酸である。上記以外の
不飽和カルボン酸としては、カルボキシル基１個あたり
の不飽和カルボン酸七ツマ−の分子量が１００以上の不
飽和カルボン酸も使用することができる。Regarding component (B) of the present invention: Examples of the polymerizable unsaturated carboxylic acid of component (B) include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, hexamaric acid, and itaconic acid; Preferred examples include acid anhydrides of dicarboxylic acids, monoalkyl esters of dicarboxylic acids, and monoamides of dicarboxylic acids. Among these, acrylic acid, methacrylic acid and itaconic acid are more preferred. As unsaturated carboxylic acids other than those mentioned above, unsaturated carboxylic acids having a molecular weight of 100 or more per carboxyl group can also be used.
これらの例を一般式にて以下に示す、この不飽和カルボ
ン酸を使用すると第２の中空微粒子の強度接着性が一段
と改良される。Examples of these are shown below in the general formula. When this unsaturated carboxylic acid is used, the adhesive strength of the second hollow particles is further improved.
（上記２つの式において、Ｒ７、Ｒ８ これら、高級カルボン酸七ツマ−の中１］ ＯＨ３ ］ 】 が特に好ましい。(In the above two formulas, R7, R8 Among these seven high carboxylic acids] OH3 ] ] is particularly preferred.
Ｃ０ＯＨ
はＨまたは炭素数１〜２０のアルキル基である）Ｃは、
下記式
％式％２
（Ｂ）成分の他の共重合可能な単量体としては、例えば
芳香族ビニル化合物、ビニルシアン化合物、アクリル酸
又はメタクリル酸のエステル脂肪族共役ジエン、有機酸
ビニル化合物、α−オレフィン類、ビニルエーテル類、
ハロゲン化ビニリデン類、ヒドロキシル基含有モノマー
、アミノ基含有モノマー、グリシジル基含有モノマ−、
アミド系モノマーおよび架橋性モノマー等が好ましく用
いられる。C0OH is H or an alkyl group having 1 to 20 carbon atoms)
Other copolymerizable monomers of the following formula % formula %2 (B) component include, for example, aromatic vinyl compounds, vinyl cyanide compounds, ester aliphatic conjugated dienes of acrylic acid or methacrylic acid, organic acid vinyl compounds, α-olefins, vinyl ethers,
Vinylidene halides, hydroxyl group-containing monomers, amino group-containing monomers, glycidyl group-containing monomers,
Amide monomers, crosslinkable monomers, and the like are preferably used.
芳香族ビニル化合物どしては例えばスチレン、α−メチ
ルスチレン、メチルスチレン、ｐ−メチルスチレン、ビ
ニルキシレン、モノクロルスチレン、ジクロルスチレン
、モノブロムスチレン、ジブロムスチレン、フルオロス
チレン、ｐ−ターシャリ−ブチルスチレン、エチルスチ
レン、ビニルナフタレン等が好ましく、特に好ましくは
、スチレン、α−メチルスチレンである。Aromatic vinyl compounds include, for example, styrene, α-methylstyrene, methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, dibromostyrene, fluorostyrene, p-tert-butyl. Styrene, ethylstyrene, vinylnaphthalene, etc. are preferred, and styrene and α-methylstyrene are particularly preferred.
ビニルシアン化合物としては例えばアクリロニトリル、
メタクリレートリル等が好ましく、より好ましくは、ア
クリロニトリルである。Examples of vinyl cyanide compounds include acrylonitrile,
Preferred are methacrylate trile and the like, more preferred is acrylonitrile.
アクリル酸又はメタクリル酸のエステル化合物としては
、例えばメチルアクリレート、エチルアクリレート、プ
ロピレンアクリレート、ブチルアクリレート、アミルア
クリレート、ヘキシルアクリレート、オクチルアクリレ
ート、２−エチルへキシルアクリレート、シクロへキシ
ルアクリレート、ドデシルアクリレート、オクタデシル
アクリレート、フェニルアクリレート、ベンジルアクリ
レート等のアクリル酸のアルキルエステル；メチルメタ
クリレート、エチルメタクリレート、プロピレンメタク
リレート、ブチルメタクリレート、アミルメタクリレー
ト、ヘキシルメタクリレート、オクチルメタクリレート
、２−エチルへキシルメタクリレート、シクロへキシル
メタクリレート、ドデシルメタクリレート、オクタデシ
ルメタクリレート、フェニルメタクリレート、ベンジル
メタクリレート等のメタクリル酸アルキルエステルを好
ましいものとして挙げられる。このうち、メチルメタク
リレート、エチルアクリレート、エチルメタクリレート
、ブチルアクリレート、ブチレンタフリレート、２−エ
チルへキシルアクリレートが好ましい。Examples of ester compounds of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, and octadecyl acrylate. , phenyl acrylate, benzyl acrylate, and other alkyl esters of acrylic acid; methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, Preferred examples include methacrylic acid alkyl esters such as octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Among these, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butylene tafrylate, and 2-ethylhexyl acrylate are preferred.
脂肪族共役ジエンとしては、例えば１．３−ブタジェン
、２−メチル−１，３−ブタジェン、２゜３−ソノチル
−１，３−ブタジエン、２−不オペンチル−１，３−ブ
タジェン、２−クロロ−１，３＝ブタジエン、２−シア
ノ−１，３−ブタジェン、置換直鎖共役ペンタジェン類
、直鎖および側鎖共役へキサジエンなどが好ましい。こ
れらのうち１．３−ブタジェンの使用が特に好ましい。Examples of aliphatic conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2゜3-sonotyl-1,3-butadiene, 2-unopentyl-1,3-butadiene, 2-chloro -1,3=butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentagenes, linear and side chain conjugated hexadiene, and the like are preferred. Among these, the use of 1,3-butadiene is particularly preferred.
有機酸ビニル化合物としては例えば酢酸ビニル、プロピ
オン酸ヒニル、ステアリン酸ビニル、などが好ましい。Preferred organic acid vinyl compounds include vinyl acetate, vinyl propionate, vinyl stearate, and the like.
その他、例えばエチレン、プロピレン、ブチレン、４−
メチルペンテン−１などのα−オレフィン類：ビニルメ
チルエーテル、ビニルエチルエーテル、ビニルイソブチ
ルエーテル、ビニルフェニルエーテルなどのビニルエー
テル類；塩化ビニリデン、フッ化ビニリデンなとの／＼
ロゲン化ヒニリデン類；ヒニルメチルケトン、ビニルピ
リジン、インブチレン、■、ｌ−塩化７ツ化エチレン、
塩化ビニル等も（Ｂ）成分の他の共重合可能な単量体と
して用いられる。Others, such as ethylene, propylene, butylene, 4-
α-olefins such as methylpentene-1; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether; vinylidene chloride, vinylidene fluoride, etc.
Logenidene hynylidenes; hinyl methyl ketone, vinyl pyridine, imbutylene,
Vinyl chloride and the like can also be used as other copolymerizable monomers of component (B).
ヒドロキシル基含有モノマーとしては、例えばアクリル
酸β−ヒドロキシエチル、メタクリル酸β−ヒドロキシ
エチル、ｎ−ヒドロキシエチルアクリルアミド、ｌ−ヒ
ドロキシプロピル−アクリレート又はメタクリレート、
ヒドロキシエチル−アクリレート又はメタクリレート等
を好ましいものとして挙げることができる。Examples of hydroxyl group-containing monomers include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, n-hydroxyethyl acrylamide, l-hydroxypropyl acrylate or methacrylate,
Preferred examples include hydroxyethyl acrylate and methacrylate.
グリシジル基含有モノマーとしては、例えばアクリル酸
グリシジル、メタクリル酸グリシジル、ビニルグリシジ
ルエーテル等を好ましいものとして挙げることができる
。Preferred examples of the glycidyl group-containing monomer include glycidyl acrylate, glycidyl methacrylate, and vinyl glycidyl ether.
アミノ基含有モノマーとしては、例えばアミノ基含有ア
クリレート又はメタクリレート、β−アミノエチルビニ
ルエーテル、ジメチルアミノエチルビニルエーテル等を
好ましいものとして挙げることができる。Preferred examples of the amino group-containing monomer include amino group-containing acrylates or methacrylates, β-aminoethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like.
アミノ基含有アクリレート又はメタクリレートとしては
、
下記式（Ｉ）
式中、ＲはＨまたはＣＨ２であり、Ｒ１及びＲ２は炭素
数１〜８好ましくは炭素数１〜３の炭化水素基であり、
Ｘは炭素数２〜４のアルキレン基である、
で表わされるものが好ましい。The amino group-containing acrylate or methacrylate has the following formula (I), where R is H or CH2, and R1 and R2 are hydrocarbon groups having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms,
X is preferably an alkylene group having 2 to 4 carbon atoms.
一般式（Ｉ）のアクリレートとしては、具体的にはジメ
チルアミノエチルアクリレート、ジメチルアミノエチル
メタクリレート、ジエチルアミノエチルアクリレート、
ジエチルアミノエチルメタアクリレート、ジプロピルア
ミノエチルメタアクリレート、メチルエチルアミノエチ
ルメタアクリレート、ジブチルアミノエチルメタアクリ
レート、ジブチルアミノプロピルメタアクリレート、ジ
エチルアミノブチルメタアクリレート、ジエチルアミノ
エチルメタアクリレート、ジオクチルアミノエチルメタ
アクリレートなどが挙げられる。Specific examples of the acrylate of general formula (I) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate,
Examples include diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, methylethylaminoethyl methacrylate, dibutylaminoethyl methacrylate, dibutylaminopropyl methacrylate, diethylaminobutyl methacrylate, diethylaminoethyl methacrylate, dioctylaminoethyl methacrylate, etc. .
これらのうち好ましいものとしてはジメチルアミノエチ
ルメタアクリレート、ジエチルアミノエチルメタアクリ
レート、ジプロピルアミノエチルメタアクリレ−１〜、
メチルエチルアミノエチルメタアクリレートなどがあげ
られる。Among these, preferred ones are dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate-1 to
Examples include methylethylaminoethyl methacrylate.
アミド第七ツマ−としては、例えばアクリルアミド、メ
タクリルアミド、ｎ−メチロールメタクリルアミド、ジ
アセトンアクリルアミド、エタクリルアミド、クロトン
アミド、イタコンアミド、メチルイタコンアミド、マレ
イン酸モノアミド、メチレンジアクリルアミドなどが挙
げられる。アクリルアミド、メタアクリルアミドが特に
好ましい。Examples of the seventh amide compound include acrylamide, methacrylamide, n-methylolmethacrylamide, diacetone acrylamide, ethacrylamide, crotonamide, itaconamide, methylitaconamide, maleic acid monoamide, methylene diacrylamide, and the like. Acrylamide and methacrylamide are particularly preferred.
架橋性モノマーとしては、例えばジビニルベンセン、エ
チレングリコールジメタクリレート、■。Examples of crosslinking monomers include divinylbenzene, ethylene glycol dimethacrylate, and ■.
３−ブチレングリコールジメタクリレート、トリメチロ
ールプロパントリメタクリレート、アリルメタクリレー
トなどのジビニル系モノマーあるいはトリビニル系七ツ
マ−を例示することができる。Examples include divinyl monomers or trivinyl monomers such as 3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate.
特にジビニルベンセン、エチレングリコールジメタクリ
レートおよび！・リメチロールプロパントリメタクリレ
ートが好ましい。Especially divinylbenzene, ethylene glycol dimethacrylate and! - Limethylolpropane trimethacrylate is preferred.
（Ｂ）成分の重合性不飽和カルボン酸対上記の如き他の
共重合可能なモノマーの組成比は０〜８０重量％重量％
−２０〜１００であり、好ましくは０．５〜５０重量％
重量％−５０〜９９．５であり、更に好ましくは１〜３
５重量％重量％−６５〜９９である。The composition ratio of component (B) polymerizable unsaturated carboxylic acid to other copolymerizable monomers as mentioned above is 0 to 80% by weight.
-20 to 100, preferably 0.5 to 50% by weight
Weight% -50 to 99.5, more preferably 1 to 3
5% by weight -65 to 99% by weight.
不飽和カルボン酸が８０重量％を越えると、重合安定性
及び得られた水性分散体の流動性が悪く、取扱時の支障
となる。又、中空微粒子の隠ぺい性、接着性、耐水性、
耐アルカリ性の物性も劣る。If the unsaturated carboxylic acid content exceeds 80% by weight, the polymerization stability and fluidity of the resulting aqueous dispersion will be poor, causing problems during handling. In addition, the concealment properties, adhesive properties, and water resistance of hollow particles
The physical properties of alkali resistance are also poor.
また、上記架橋性モノマーは（Ｂ）成分１００重量部に
対して０．５〜２０重量％、好ましくは１〜５重量％の
範囲で使用すると第２の中空微粒子の隠ぺい性、耐溶剤
性、耐水性強度のバランスが１段と改良される。In addition, when the crosslinking monomer is used in an amount of 0.5 to 20% by weight, preferably 1 to 5% by weight, based on 100 parts by weight of component (B), the second hollow fine particles have good hiding properties and solvent resistance. The balance of water resistance and strength is further improved.
本発明の（Ｃ）工程について：
本発明の（Ｃ）工程は第１の中空微粒子（Ａ）とモノマ
ー混合物（Ｂ）の合計重量１００重量部当り５重量部以
下の乳化剤及び／又は分散剤の存在下、水媒体中で重合
することで、該第１の中空ポリマー微粒子（Ａ）の表面
にモノマー又はモノマー混合物（Ｂ）の重合体被膜を生
成せしめて平均粒子径が０．１〜２０μｍの範囲にある
第２の中空ポリマー微粒子を形成する工程である。Regarding step (C) of the present invention: In step (C) of the present invention, 5 parts by weight or less of an emulsifier and/or a dispersant are added per 100 parts by weight of the first hollow fine particles (A) and the monomer mixture (B). By polymerizing in an aqueous medium in the presence of the polymer, a polymer film of the monomer or monomer mixture (B) is formed on the surface of the first hollow polymer fine particles (A), and the average particle diameter is 0.1 to 20 μm. This is a step of forming second hollow polymer fine particles within the range.
上記製造方法に於いて、モノマー又はモノマー混合物（
Ｂ）として重合性不飽和カルボン酸を含有する単量体混
合物であるときは、重合時のｐＨは７以下であることが
特に好ましい。In the above production method, the monomer or monomer mixture (
When B) is a monomer mixture containing a polymerizable unsaturated carboxylic acid, the pH during polymerization is particularly preferably 7 or less.
重合工程に於いて、モノマー又はモノマーＲ合物（Ｂ）
の添加方法は、第１の中空ポリマー微粒子（Ａ）とモノ
マー又はモノマー混合物（Ｂ）を撹拌混合し重合させる
方法、モノマー混合物（Ｂ）を第１の中空ポリマー微粒
子（Ａ）の存在する重合系へ連続的あるいは分割的に供
給し重合を行なわせるインクレメント重合法などがある
。効率的に内孔を有するポリマー粒子表面に重合性モノ
マーを共重合させるには、インクレメント重合法が、安
定に重合するためにも好ましい。In the polymerization step, monomer or monomer R compound (B)
The addition method includes a method of stirring and mixing the first hollow polymer fine particles (A) and the monomer or monomer mixture (B) and polymerizing the mixture, and adding the monomer mixture (B) to the polymerization system in which the first hollow polymer fine particles (A) are present. There is an incremental polymerization method in which polymerization is carried out by supplying the polymer continuously or in parts. In order to efficiently copolymerize a polymerizable monomer onto the surface of a polymer particle having internal pores, an incremental polymerization method is preferable in order to achieve stable polymerization.
中空微粒子の重合に際しては、アニオン型、ノニオン型
、カチオン型、両性型などの乳化剤、および／または分
散剤（懸濁保護剤）を使用する。In the polymerization of hollow fine particles, anionic, nonionic, cationic, amphoteric, etc. emulsifiers and/or dispersants (suspension protectants) are used.
これらは１種もしくは２種以上併用することができる。These can be used alone or in combination of two or more.
乳化剤としては、例えばロジン酸カリウム、ロジン酸ナ
トリウム等のロジン酸塩；オレイン酸カリウム、ラウリ
ン酸カリウム、ラウリン酸ナトリウム、ステアリン酸ナ
トリウム、ステアリン酸カリウム等の脂肪酸のナトリウ
ム、カリウム塩及びラウリル硫酸ナトリウム等の脂肪族
アルコールの硫酸エステル塩ニドデシルベンゼンスルホ
ン酸ナトリウム等のアルキルアリルスルホン酸塩、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
酸のホルマリン縮金物塩などのアニオン型乳化剤；ポリ
エチレングリコールのアルキルエステル型、アルキルエ
ーテル型、アルキルフェニルエーテル型などの非イオン
型乳化剤が好ましい。Examples of emulsifiers include rosinate salts such as potassium rosinate and sodium rosinate; sodium and potassium salts of fatty acids such as potassium oleate, potassium laurate, sodium laurate, sodium stearate, and potassium stearate, and sodium lauryl sulfate. anionic emulsifiers such as sulfuric ester salts of aliphatic alcohols, alkylaryl sulfonates such as sodium nidodecylbenzenesulfonate, sodium dialkyl sulfosuccinates, and formalin condensate salts of naphthalene sulfonic acid; alkyl ester types of polyethylene glycol, alkyl ethers; Nonionic type emulsifiers such as type, alkyl phenyl ether type and the like are preferred.
中でも、ラウリル硫酸ナトリウム、ドデシルベンゼンス
ルホン酸ナトリウム、ジオクチ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金物塩、ポ
リエチレングリコールのアルキルフェニルエーテル型が
、好ましい。Among these, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, formalin condensate salt of naphthalenesulfonic acid, and alkylphenyl ether type polyethylene glycol are preferred.
カチオン型乳化剤としては、第４級アンモニウム塩型な
どがあるが、水性分散体をカチオン型とする場合に、単
独又は、ノニオンと併用して使用される。Examples of cationic emulsifiers include quaternary ammonium salt type emulsifiers, and when the aqueous dispersion is made into a cationic emulsifier, they are used alone or in combination with a nonionic emulsifier.
また分散剤としては、例えばポリアクリル酸、ポリメタ
クリル酸、ポリビニルスルホン酸、ポリビニルアルコー
ル、ポリビニルピロリドン、ポリエチレングリコールな
どの親水性合成高分子物質；ゼラチン、水溶性澱粉など
の天然親水性高分子物質；カルボキシメチルセルロース
などの親水性半合成高分子物質などを挙げることができ
る。Examples of dispersants include hydrophilic synthetic polymer substances such as polyacrylic acid, polymethacrylic acid, polyvinyl sulfonic acid, polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol; natural hydrophilic polymer substances such as gelatin and water-soluble starch; Examples include hydrophilic semi-synthetic polymeric substances such as carboxymethylcellulose.
乳化剤及び／又は分散剤の使用量は５重量部以下、好ま
しくは２重量部以下、更に好ましくは１重量部以下であ
る。５重量部を超えると重合中の新粒子発生により、本
発明の第２の中空微粒子の生産効率が低下し、更に隠ぺ
い性、光沢が低下するので好ましくない。The amount of emulsifier and/or dispersant used is 5 parts by weight or less, preferably 2 parts by weight or less, more preferably 1 part by weight or less. If the amount exceeds 5 parts by weight, the production efficiency of the second hollow fine particles of the present invention decreases due to the generation of new particles during polymerization, and furthermore, the hiding power and gloss decrease, which is not preferable.
重合開始剤としては、例えばクメンハイドロパーオキサ
イド、ジイソプロピルベンゼンハイドロパーオキサイド
、パラメンタンハイドロパーオキサイド等で代表される
有機ハイドロパーオキサイド類と含糖ピロリン酸処方、
スルホキシレート処方、含糖ピロリン酸処方／スルホキ
シレート処方の混合系処方等で代表される還元剤との組
合わせによるレドックス系の開始剤；更に過硫酸カリウ
ム、過硫酸アンモニウム等の過硫酸塩；アゾビスイソブ
チロニトリル、ベンゾイルパーオキサイド、ラウロイル
パーオキサイド等を使用することができる。Examples of polymerization initiators include organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, and sugar-containing pyrophosphoric acid formulations.
Redox initiators in combination with reducing agents, such as sulfoxylate formulations and mixed formulations of sugar-containing pyrophosphate formulations/sulfoxylate formulations; and persulfates such as potassium persulfate and ammonium persulfate; Azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, etc. can be used.
好ましくは、過硫酸カリウム、過硫酸アンモニウム等の
過硫酸塩、アゾビスイソブチロニトリル、ベンゾイルパ
ーオキサイドに、必要に応じて還元剤を組合わせたもの
である。特に好ましくは過硫酸カリウム、過硫酸アンモ
ニウム等の過硫酸塩である。これらの重合開始剤は第１
の中空微粒子表面にラジカルが集中しやすいため（Ｂ）
成分による被膜の生成が効率良く行なわれる。重合開始
剤量は第１の中空微粒子（Ａ）とモノマー又はモノマー
混合物（Ｂ）の合計量に対して、好ましくは０，０５〜
２重量部、更に好ましくは０．０５〜０．８重量部であ
る。この範囲で使用すると耐水性、耐アルカリ性に優れ
た第２の中空ポリマー微粒子が得られる。Preferably, a persulfate such as potassium persulfate or ammonium persulfate, azobisisobutyronitrile, or benzoyl peroxide is combined with a reducing agent if necessary. Particularly preferred are persulfates such as potassium persulfate and ammonium persulfate. These polymerization initiators are the first
Because radicals tend to concentrate on the surface of hollow fine particles (B)
A film is efficiently formed by the components. The amount of polymerization initiator is preferably 0.05 to 0.05 to the total amount of the first hollow fine particles (A) and the monomer or monomer mixture (B).
The amount is 2 parts by weight, more preferably 0.05 to 0.8 parts by weight. When used within this range, second hollow polymer fine particles having excellent water resistance and alkali resistance can be obtained.
重合温度としては、通常５〜９５℃が良好であり、特に
５０〜９０°Ｃが好ましい。The polymerization temperature is usually 5 to 95°C, particularly preferably 50 to 90°C.
その他必要に応じて連鎖移動剤を併用することができる
。Other chain transfer agents may be used in combination if necessary.
連鎖移動剤としては、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、オクチルメルカプタン、１〜ヘキシルメルカプタン
などのメルカプタン類、四塩化炭素、臭化エチレンなど
のハロゲン系化合物を挙げることができる。Examples of the chain transfer agent include mercaptans such as t-dodecylmercaptan, octylmercaptan, n-tetradecylmercaptan, octylmercaptan, and 1-hexylmercaptan, and halogen compounds such as carbon tetrachloride and ethylene bromide. .
本発明の乳化重合においては、重合系のｐｕにより、重
合安定性および第２の中空微粒子の粒子径分布、内径／
外径比が少なからず左右される。In the emulsion polymerization of the present invention, the polymerization stability and the particle size distribution of the second hollow fine particles, inner diameter/
It depends to a large extent on the outer diameter ratio.
ｐＨ７以下の場合は、上記項目について良好であり、目
的とする第２の中空微粒子が得られる。ｐＨか７を越え
る場合では、モノマー又はモノマー混合物（Ｂ）に重合
性不飽和カルボン酸を含まない時は上記項目について、
同様に問題なく良好であるか、重合性不飽和カルボン酸
を含む場合は、重合安定性か低下する傾向か見られ好ま
しくない。When the pH is 7 or less, the above items are satisfactory, and the desired second hollow fine particles can be obtained. If the pH exceeds 7, and the monomer or monomer mixture (B) does not contain a polymerizable unsaturated carboxylic acid, the above items:
Similarly, if it is good without any problems, or if it contains a polymerizable unsaturated carboxylic acid, the polymerization stability tends to decrease, which is not preferable.
第１の中空微粒子（Ａ）として前述の特開昭６２−１２
７３３６て得られた中空微粒子の水分散体を使用すると
、そのｐＨか７以下である為、該中空微粒子の表面に形
成させる重合体のモノマーを制限なく使用でき、極めて
好ましい。As the first hollow fine particles (A), the above-mentioned JP-A-62-12
The use of an aqueous dispersion of hollow fine particles obtained by the method No. 7336 is extremely preferable since its pH is 7 or less, so that the monomer of the polymer to be formed on the surface of the hollow fine particles can be used without restriction.
一方、アルカリ中和膨潤により、内孔を生しさせて中空
微粒子を製造する方法で得られた水分散体のｐＨは当然
ながら７を越えるから、特にモノマー又はモノマー混合
物（Ｂ）に重合性不飽和カルボン酸か含まれる場合には
該水分散体の使用は好ましくない。又、このもののｐＨ
を下けるべく、炭酸水素すＩ〜ツリウムようなバッファ
ーあるいは酸を添加すると、重合安定性の不良を招く為
、やはり、第１の中空微粒子としてアルカリ中和膨潤で
製造した粒子を用いるのは好ましくない。On the other hand, since the pH of the aqueous dispersion obtained by the method of producing hollow particles by producing inner pores through alkali neutralization and swelling naturally exceeds 7, the monomer or monomer mixture (B) has no polymerizable properties. Use of the aqueous dispersion is not preferred if saturated carboxylic acids are present. Also, the pH of this thing
If a buffer or acid such as hydrogen carbonate or thulium is added to lower the reaction temperature, the polymerization stability will be deteriorated, so it is still preferable to use particles produced by alkali neutralization swelling as the first hollow particles. do not have.
以上のようにして得られた本発明の水分散体（Ｃ）は、
外径か０．１〜２０μｍ１内径が外径の０．１〜０．８
５倍であることが好ましい。外径が０．１μｍ未満のも
のは、光散乱助剤として用いた時の隠ぺい性が劣り、２
０μｍを越えるものは、重合安定性が悪く、又、重合生
新粒子が発生し、目的とする隠ぺい性、と光沢をはじめ
とする各種の物性のバランスがとれない。The aqueous dispersion (C) of the present invention obtained as described above is
Outer diameter is 0.1 to 20 μm 1 Inner diameter is 0.1 to 0.8 of the outer diameter
Preferably it is 5 times. Those with an outer diameter of less than 0.1 μm have poor hiding properties when used as a light scattering aid;
If it exceeds 0 μm, polymerization stability is poor, and new polymerized particles are generated, making it impossible to achieve the desired balance between hiding properties and various physical properties such as gloss.
又、内径が外径の０．１倍未満である場合は、隠ぺい性
がかなり劣り好ましくなく、０．８５倍を越えるものは
隠ぺい性と接着性、光沢、強度のバランスが劣り、好ま
しくない。Moreover, if the inner diameter is less than 0.1 times the outer diameter, the hiding property will be considerably poor, which is not preferable, and if it exceeds 0.85 times, the balance between hiding property, adhesiveness, gloss, and strength will be poor, which is not preferable.
本発明の水性分散体（Ｃ）の固形分としては制限はない
が各用途の配合物の固形分から見て、通常ｌＯ〜６５％
であることが好ましい。There is no limit to the solid content of the aqueous dispersion (C) of the present invention, but considering the solid content of the formulation for each use, it is usually 10 to 65%.
It is preferable that
尚、本発明の水性分散体のポリマー粒子が、孔を有して
いるかどうかは、簡単に確認できる。透過型電子顕微鏡
で、一般的には、確認できるし、比重を測定することに
よっても確認できる。Note that it can be easily confirmed whether the polymer particles of the aqueous dispersion of the present invention have pores. It can generally be confirmed using a transmission electron microscope, and also by measuring specific gravity.
４ト発明で得られた水性分散体を乾燥することによって
粉末化することかできる。粉末化は、一般に行なわれて
いる水性分散体の粉末化法で粉末化でき、例えは１３０
〜１６０°Ｃにおける噴霧乾燥、熱風雰囲気中で例えは
、５０〜７０°Ｃでのトレイ乾燥なとである。乾燥前の
水性分散体の固形分は、２０％以上か好ましい。得られ
た本発明水性分散体の粉末の粒子径は、使用した水性分
散体の粒子径とほぼ同等である。The aqueous dispersion obtained in the fourth invention can be powdered by drying. Powdering can be done by a commonly used aqueous dispersion powdering method, for example, 130
Spray drying at ~160°C, tray drying at 50-70°C in a hot air atmosphere. The solid content of the aqueous dispersion before drying is preferably 20% or more. The particle size of the obtained powder of the aqueous dispersion of the present invention is approximately the same as the particle size of the aqueous dispersion used.
このようにして得られた粉末は、このものか有機溶媒に
不溶である場合は、有機溶媒系塗料にも使用することが
てきる。The powder thus obtained can also be used for organic solvent-based paints if it is insoluble in organic solvents.
上記、本発明の水性分散体及びその粒子は、隠ぺい性と
、光沢、接着性、耐水性、耐溶媒性、耐熱性、等の諸物
性とのバランスに優れたプラスデックピグメンＩ・（有
機性樹脂顔料）に有用であり、塗料、紙用被覆剤、イン
キ、接着剤、粘着剤、プライマー剤、皮革処理剤なとに
応用できる。又、内包性を利用し、ポリマー粒子の内孔
に香料、医薬、農薬、染料、洗剤、油脂、食品、酵素、
液晶、防錆剤、触媒、難燃剤、老化防止剤、接着剤など
を用途に応してその有効成分を浸漬処理、減圧、加圧浸
漬処理等の手段により封入でき、内部に含まれた有用成
分に応じて各種用途に利用することかできる。The above aqueous dispersion and particles thereof of the present invention have an excellent balance of hiding properties and various physical properties such as gloss, adhesiveness, water resistance, solvent resistance, and heat resistance. It is useful for paints, paper coatings, inks, adhesives, pressure-sensitive adhesives, primers, leather treatment agents, etc. In addition, by utilizing the encapsulation property, the inner pores of polymer particles can contain fragrances, medicines, pesticides, dyes, detergents, oils and fats, foods, enzymes, etc.
The active ingredients of liquid crystals, rust preventives, catalysts, flame retardants, anti-aging agents, adhesives, etc. can be encapsulated by immersion treatment, reduced pressure, pressure immersion treatment, etc. depending on the application, and the useful ingredients contained inside can be encapsulated. It can be used for various purposes depending on the ingredients.
［実施例］
次に実施例により本発明をさらに詳細に説明するが、こ
れにより本発明が制限されるものではない。なお、以下
の記載において「％」及び「部」は、重量％及び重量部
を表わす。[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In addition, in the following description, "%" and "part" represent weight % and weight part.
第１の中空微粒子（Ａ）の製造：
（１，）Ａ−１の製造
■ 異種ポリマー（１〕）の製造 （ｂ−１）スヂレン
８０部、メタクリル酸メチル１７部、メタクリル酸３部
及びｔ−ドデシルメルカプタン７部を、水２００部にラ
ウリル硫酸ナトリウム０゜５部及び過硫酸カリウムＬＯ
部を溶かした水溶液に入れ、撹拌しなから７０℃で４時
間重合してポリマー粒子を得た。このポリマー粒子は平
均粒子径０．２μｍ、ＧＰＣによるポリスチレン換算の
数平均分子量６，０００であった。これをｂ−■とする
。Production of first hollow fine particles (A): (1,) Production of A-1 ■ Production of heterogeneous polymer (1) (b-1) 80 parts of sutyrene, 17 parts of methyl methacrylate, 3 parts of methacrylic acid, and t - 7 parts of dodecyl mercaptan, 0.5 parts of sodium lauryl sulfate and LO of potassium persulfate in 200 parts of water.
The polymer particles were added to an aqueous solution in which 1 part was dissolved and polymerized at 70°C for 4 hours without stirring to obtain polymer particles. The polymer particles had an average particle diameter of 0.2 μm and a number average molecular weight of 6,000 in terms of polystyrene by GPC. This is referred to as b-■.
■ 第１の中空微粒子（Ａ）の製造（Ａ、−１）次にこ
のポリマー粒子分散体（ｂ−１）を種ポリマー粒子とし
て用い、このポリマー粒子を固形分で１０部、ポリオキ
シエチレンノニルフェニルエーテル０．１部、ラウリル
硫酸ナトリウム０．３部及び過硫酸カリウム０．５部と
水３９０部を反応容器に仕込んだ。これにメタクリル酸
メチル７５部、ジビニルベンゼン（純品換算）２０部及
びアクリル酸５部の混合物を加えて３０°Ｃで１時間撹
拌したところ、上記物質は種ポリマー粒子にほぼ完全に
吸収された。これを７０°Ｃで５時間撹拌しなから重合
したところ、重合収率９９％で水を粒子内部に含むカプ
セル粒子の分散液が得られた。■ Production of the first hollow fine particles (A) (A, -1) Next, using this polymer particle dispersion (b-1) as a seed polymer particle, 10 parts of the solid content of the polymer particles, polyoxyethylene nonyl 0.1 part of phenyl ether, 0.3 part of sodium lauryl sulfate, 0.5 part of potassium persulfate, and 390 parts of water were charged into a reaction vessel. When a mixture of 75 parts of methyl methacrylate, 20 parts of divinylbenzene (purity equivalent) and 5 parts of acrylic acid was added to this and stirred at 30°C for 1 hour, the above substance was almost completely absorbed into the seed polymer particles. . When this was polymerized while stirring at 70°C for 5 hours, a dispersion of capsule particles containing water inside the particles was obtained with a polymerization yield of 99%.
この分散液を乾燥し、透過型電子顕微鏡で観察したとこ
ろ、このポリマー粒子は、中央部が透けている完全な球
形の中空ポリマー粒子であった。この中空粒子は外径が
０．４μｍ、内径が０．３μｍであった。これをＡ−１
とした。When this dispersion was dried and observed under a transmission electron microscope, the polymer particles were completely spherical hollow polymer particles with a transparent center. The hollow particles had an outer diameter of 0.4 μm and an inner diameter of 0.3 μm. This is A-1
And so.
このようにして得た第１の中空微粒子（Ａ）を以後に述
べる本発明の中空微粒子製造におけるシードとして用い
た。The first hollow fine particles (A) thus obtained were used as seeds in the production of hollow fine particles of the present invention described below.
（２）Ａ−２〜６．８．９．１１１３及びｂ−２〜７の
製造：
異種ポリマー粒子ｂ−１及び中空微粒子Ａ−１製造方法
中のモノマー、異種ポリマー使用量などを第−表に示し
たものにかえたほかは、ｂ−１及びＡ−１と同様な方法
で重合を行ない、Ａ−２〜６．８．９、ｌ’Ｌ１３およ
び異種ポリマーｂ−２〜７を得た。(2) Production of A-2 to 6.8.9.1113 and b-2 to 7: Table 1 shows the amount of monomers and different polymers used in the method for producing different polymer particles b-1 and hollow fine particles A-1. Polymerization was carried out in the same manner as b-1 and A-1, except that the polymers were changed to those shown in , to obtain A-2 to 6.8.9, l'L13, and different polymers b-2 to 7. .
ただし、Ａ−５，６、は、それぞれの異種ポリマーｂ−
２（１０部）に前者はトルエン１０部、後者はジブチル
フタレート１５部吸収させたのちに重合したものである
。重合条件と結果は第−表に示した。However, A-5, 6, each different polymer b-
2 (10 parts), the former was made to absorb 10 parts of toluene, and the latter was made to absorb 15 parts of dibutyl phthalate, and then polymerized. The polymerization conditions and results are shown in Table 1.
（３）Ａ−７の製造
＝４３−
モノマー成分：
４−ビニルピリジン ； ５０部ジビニルベンゼ
ン ； ２部スチレン ；
２８部ブチルアクリレート ： ２０部芯材
の油性物質：
トルエン ； １０部重合開始剤：
３．５．５−トリメチルへキサ
ノイルパーオキサイド ２部［パーロイル３
５５、日本油脂（株）社製］以上の物質を混合して油性
溶液を調製した。ついでこの油性溶液を、ポリビニルア
ルコール（ゴーセノールＧＨ２０、日本合成化学（株）
製）１０部を溶解した水３５０部に加え、この系を直径
５ｃｍのプロペラ型撹拌翼を用いて回転数５，０００
ｒ、ｐ、ｍ、で１５分間撹拌することによって、前記油
性溶液をその油滴の径が５〜１５μｍとなるよう水中に
分散させた。このようにして得られた懸濁液を容量２ａ
の反応容器に入れ、窒素雰囲気下において回転数１２Ｏ
ｒ、ｐ劃、で懸濁液を撹拌しながら、温度７０℃で１５
時間にわたり重合を行ない、ポリマー粒子を製造した。(3) Production of A-7 = 43- Monomer components: 4-vinylpyridine; 50 parts divinylbenzene; 2 parts styrene;
28 parts Butyl acrylate: 20 parts Core material oily substance: Toluene; 10 parts Polymerization initiator: 3.5.5-trimethylhexanoyl peroxide 2 parts [Perloyl 3
55, manufactured by Nippon Oil & Fats Co., Ltd.] The above substances were mixed to prepare an oily solution. Next, this oily solution was mixed with polyvinyl alcohol (Gohsenol GH20, Nippon Gosei Kagaku Co., Ltd.).
Add 10 parts of (manufactured by) to 350 parts of water, and stir this system at 5,000 rotations using a propeller-type stirring blade with a diameter of 5 cm.
The oil solution was dispersed in water by stirring at r, p, m for 15 minutes so that the oil droplets had a diameter of 5 to 15 μm. The suspension thus obtained has a volume of 2a
into a reaction vessel and rotated at 120 rotations under a nitrogen atmosphere.
While stirring the suspension with
Polymerization was carried out for a period of time to produce polymer particles.
この反応における重合収率は９８％であった。The polymerization yield in this reaction was 98%.
得られたポリマー粒子を光学顕微鏡によって観察したと
ころ、中空ポリマー粒子であった。この中空粒子は、外
径１３μｍ１内径は９μｍであった。When the obtained polymer particles were observed using an optical microscope, they were found to be hollow polymer particles. The hollow particles had an outer diameter of 13 μm and an inner diameter of 9 μm.
これをＡ−７とした。This was designated as A-7.
（４） Ａ−１０，１２の製造
Ａ−７の製造方法のモノマー組成及び油性物質トルエン
の使用量を第−表に示したものにかえたほかはＡ−７と
同様な方法で重合を行ないＡ−１０，１２を得た。(4) Production of A-10 and 12 Polymerization was carried out in the same manner as A-7 except that the monomer composition and the amount of oily substance toluene used in the production method of A-7 were changed to those shown in Table 1. A-10 and A-12 were obtained.
第２の中空微粒子（本発明の中空微粒子）の製造：実施
例１
前記の方法で準備された中空粒子水性分散体Ａ−１をシ
ード粒子に使用し、固形分で２０部、水１２７部、過硫
酸カリウム０．７部を２Ｑの反応容器に入れ、窒素雰囲
気下で温度を８５°Ｃに上昇させ、次のモノマーエマル
ジョンを３時間にわたり連続滴下した。Production of second hollow particles (hollow particles of the present invention): Example 1 Hollow particle aqueous dispersion A-1 prepared by the above method was used as seed particles, solid content was 20 parts, water was 127 parts, 0.7 parts of potassium persulfate was placed in a 2Q reaction vessel, the temperature was raised to 85°C under a nitrogen atmosphere, and the following monomer emulsion was continuously added dropwise over 3 hours.
モノマーエマルジョン：
水 ４
０部、アクリル酸ブチル ５部
、メタクリル酸メヂル ８９部、メ
タクリル酸 ５部・Ｎ−メ
チロールメタクリルアミド １部およびドデシ
ルベンゼンスルホン酸ナトリウム ０，３部滴下終了
後２時間その温度を保ち、その後冷却した。得られた分
散体には凝固物はなかった。分散体の粒子径をナノザイ
ザー（コールタ−社、Ｎ−４モデル）で測定した所、０
．６３μｍであった。Monomer emulsion: Water 4
0 parts, butyl acrylate 5 parts, medyl methacrylate 89 parts, methacrylic acid 5 parts, N-methylolmethacrylamide 1 part and sodium dodecylbenzenesulfonate 0.3 parts After completion of the dropwise addition, the temperature was maintained for 2 hours, and then cooled. . There was no coagulum in the resulting dispersion. The particle size of the dispersion was measured using a Nanosizer (Coulter Co., model N-4) and was found to be 0.
．． It was 63 μm.
得られた分散体を乾燥し、透過型電子顕微鏡で観察した
所、第１の中空微粒子表面にポリマー層がコートされて
いた。この中空粒子は外径が０．６３μｍ１ 内径か
０．３μｍであった。又新核子の発生はなく、すべての
粒子か中空を有していた。製造用件と結果を第二衣に示
す。When the obtained dispersion was dried and observed under a transmission electron microscope, it was found that the surfaces of the first hollow particles were coated with a polymer layer. The hollow particles had an outer diameter of 0.63 μm and an inner diameter of 0.3 μm. Also, no new nucleons were generated, and all particles had hollow spaces. The manufacturing conditions and results are shown in the second picture.
実施例２．３．６．９、比較例１〜５
実施例１において、一部の条件を第二衣の実施例２．３
．６．９及び比較例１〜５の欄に記載の条件に変えたほ
かは、実施例１と全く同様に重合しＩこ。Example 2.3.6.9, Comparative Examples 1 to 5 In Example 1, some conditions were changed to Example 2.3 for the second coating.
．． Polymerization was carried out in exactly the same manner as in Example 1, except that the conditions were changed to those described in 6.9 and Comparative Examples 1 to 5.
実施例４
１００ａのステンレス製耐圧容器に水１５０部、過硫酸
カリウム１．０部、亜硫酸水素ナトリウム０．４部、ド
デシルベンゼンスルホン酸ナトリウム０．５Ｎ、ポリオ
キシエチレンノニルフェニルエーテル（ＥＯ＝３０モル
）０．１部、及びシード粒子として前記Ａ−３を固形分
換算で４０部を仕込み、撹拌しながら窒素雰囲気下、７
０°Ｃに昇温し、以下のモノマー混合物を１２時間わた
り連続的に滴下した。Example 4 In a 100a stainless steel pressure-resistant container, 150 parts of water, 1.0 part of potassium persulfate, 0.4 part of sodium bisulfite, 0.5N of sodium dodecylbenzenesulfonate, and polyoxyethylene nonylphenyl ether (EO = 30 mol) ), and 40 parts of the above A-3 in terms of solid content as seed particles, and while stirring, under a nitrogen atmosphere,
The temperature was raised to 0°C, and the following monomer mixture was continuously added dropwise over 12 hours.
モノマー混合物：
スチレン ５０部、
■、３−ブタジェン ４０部、
メタクリル酸 ５都及び
アクリエステルＨＨ５部
ざらにモノマー添加終了後５時間８０°Ｃにおいて熟成
を行ない、その後冷却した。得られた分散体６こは凝固
物はなかった。分散体の粒子径は０．５５μｍ、乾燥後
のポリマー粒子の外径は０．５４μｍ１内径０．３μｍ
の中空粒子てあり、新核子の発生はなかった。Monomer mixture: 50 parts of styrene, 40 parts of 3-butadiene, 5 parts of methacrylic acid and 5 parts of acrylic ester HH. After the addition of the monomers, the mixture was aged at 80°C for 5 hours, and then cooled. There was no coagulum in the six dispersions obtained. The particle size of the dispersion is 0.55 μm, and the outer diameter of the polymer particles after drying is 0.54 μm and the inner diameter is 0.3 μm.
There were hollow particles, and no new nucleons were generated.
実施例５．７および８
実施例４において、一部の条件を第二衣の実施例５．７
．８の欄に記載の条件に変えたほがは、実施例４と全く
同様に重合した。Examples 5.7 and 8 In Example 4, some conditions were changed to Example 5.7 for the second garment.
．． Polymerization was carried out in exactly the same manner as in Example 4 except that the conditions were changed to those described in column 8.
実施例１０
中空粒子水性分散体Ａ−１をシード粒子に使用し、固形
分で５００部、水１４００部、ドデシルベンゼンスルホ
ン酸すｌ・リウム０．７部、ポリオキンエチレンノニル
フェニルエーテル（ＥＯ＝３０モル）０．１部を２０．
の反応容器に入れた。Example 10 Hollow particle aqueous dispersion A-1 was used as seed particles, solid content 500 parts, water 1400 parts, dodecylbenzenesulfonic acid sulfur/lium 0.7 parts, polyoxine ethylene nonylphenyl ether (EO= 30 mol) 0.1 part to 20.
into a reaction vessel.
これにアクリル酸−ｎ−ブチル５部、メタクリル酸メチ
ル８９部、メタクリル酸６部の混合物を加えて、４０℃
で１時間撹拌し、上記モノマー混合物をシード中空ポリ
マー粒子にほぼ完全に吸収させた。これにペンソイルパ
ーオキサイド１．０部、亜硫酸水素すトリウム０．５部
、を添加し、７０°Ｃに昇温し、５時間重合し、その後
冷却した。得られた分散体には凝固物はなく、乾燥後の
ポリマー粒子の外径は０．４１μｍ１内径は０．３μｍ
の中空粒子であり、新核子の発生はなかった。A mixture of 5 parts of n-butyl acrylate, 89 parts of methyl methacrylate, and 6 parts of methacrylic acid was added to this, and the mixture was heated to 40°C.
The monomer mixture was stirred for 1 hour at a temperature such that the monomer mixture was almost completely absorbed into the seed hollow polymer particles. To this were added 1.0 part of pensoyl peroxide and 0.5 part of sodium bisulfite, the temperature was raised to 70°C, polymerization was carried out for 5 hours, and then cooled. There was no coagulum in the obtained dispersion, and the outer diameter of the polymer particles after drying was 0.41 μm and the inner diameter was 0.3 μm.
It was a hollow particle, and no new nucleons were generated.
比較例６および７
実施例１の第１の中空微粒子分散体のかわりに下記に示
す通常のポリマー粒子分散体を使用したものであり、得
られたポリマー粒子の粒子径は、０．６４μｍで内孔は
なかった。これを比較例６とする。Comparative Examples 6 and 7 The following ordinary polymer particle dispersion was used instead of the first hollow fine particle dispersion of Example 1, and the particle diameter of the obtained polymer particles was 0.64 μm. There were no holes. This is referred to as Comparative Example 6.
シードのポリマー粒子分散体Ｃ−１： 通常の乳化重合で製造された水性分散 体。Seed polymer particle dispersion C-1: Aqueous dispersions produced by conventional emulsion polymerization body.
粒子径０．４ μｍ、 ｐｔ（７，２、固形分４０％。Particle size 0.4 μm, pt (7,2, solid content 40%.
組成は、アクリル酸ブチル／メタクリ ル酸メチル／スチレン／アクリル酸− ４５／Ｉ Ｏ／４２／３で、内孔は存在しない。The composition is butyl acrylate/methacrylate. Methyl phosphate/styrene/acrylic acid- 45/I O/42/3 with no internal pores.
上記方法のシードのポリマー粒子の種類及び使用量を第
二表と下記のものにかえたものを比較例７とした。Comparative Example 7 was prepared by changing the type and amount of polymer particles used in the seed in the above method to those shown in Table 2 and below.
シードのポリマー粒子分散体Ｃ−２； 通常の懸濁重合で製造された水性分散 体。Seed polymer particle dispersion C-2; Aqueous dispersion produced by conventional suspension polymerization body.
粒子径４μｍ５ｐＨ７，８固形分４５％。Particle size: 4 μm, pH: 7.8, solid content: 45%.
組成はアクリル酸エチル／スチレン／ アクリル酸−２０／７９／ｌで、内孔 は存在しない。Composition is ethyl acrylate/styrene/ Acrylic acid - 20/79/l, inner pore does not exist.
比較例８．９およびＩＯ
前記Ａ−１の中空微粒子および市販のポリマー微粒子（
Ｒｏｈｍ、 ＆ Ｈａａｓ社製０Ｐ−８４（Ｄ−１）お
よび旭化成社プラスチックピグメントＡＫ８８０１（Ｄ
−２）をそれぞれ単味で使用した例をそれぞれ比較例８
．９及びｌＯとした。Comparative Example 8.9 and IO Hollow fine particles of A-1 and commercially available polymer fine particles (
Rohm, & Haas 0P-84 (D-1) and Asahi Kasei Plastic Pigment AK8801 (D
Comparative Example 8 shows an example in which -2) is used alone.
．． 9 and lO.
［応用例１
実施例１〜１０、比較例１〜１０の各水性分散体を固形
分で６０部、ルチル型二酸化チタンの７１％水分散体を
固形分で４０部、バインダーとしてアクリル系共重合エ
マルジョン（日本合成ゴム（株）製、ＪＳＲＡＥ３１５
）を固形分で１５０部、２．２．４−トリメチル−１，
３−ベンタンジオールモノイソブチレート（デキサノー
ルＣ５−１２チツソ（株）製）７部、エチレングリコー
ル３部、β−ナフタレンスルホン酸ホルマリン縮金物の
ナトリウム塩２部、ヒドロキシエチルセルロース１．５
部、水１５０部からなる配合物を配合し、粘度が一定に
なるまで撹拌した。このようにして各塗料配合物を作製
した。[Application Example 1 60 parts of each aqueous dispersion of Examples 1 to 10 and Comparative Examples 1 to 10 as a solid content, 40 parts of a 71% aqueous dispersion of rutile titanium dioxide as a solid content, and acrylic copolymerization as a binder. Emulsion (manufactured by Japan Synthetic Rubber Co., Ltd., JSRAE315
), 150 parts solids, 2.2.4-trimethyl-1,
7 parts of 3-bentanediol monoisobutyrate (Dexanol C5-12 manufactured by Chitsuso Co., Ltd.), 3 parts of ethylene glycol, 2 parts of sodium salt of β-naphthalenesulfonic acid formalin condensate, 1.5 parts of hydroxyethyl cellulose
150 parts of water was blended and stirred until the viscosity was constant. Each paint formulation was prepared in this manner.
上記各種塗料をモレスト隠幣カチャート上およびガラス
板上に塗布し、同一の厚さの塗膜となし３日間風乾した
。第二表にこれらの塗膜の物理学的な性質を示した。尚
、試験条件は以下の通り。The above-mentioned various paints were applied on a Moresto covert carchart and a glass plate to form a coating film of the same thickness and air-dried for 3 days. Table 2 shows the physical properties of these coatings. The test conditions are as follows.
（試験条件）
５ｌ−
（１）隠ぺい率；
隠ぺい本試験紙（日本テストパネル工
業（株）製）に６ミルアプリケーター
にて塗布し、２０°０１６０％ＲＨ中にて５日乾燥後村
上式光沢計にて４５゜
１０°の光沢を試験紙の黒白部につい
て測定しそれらの比率より下式を用い
て算出した。（ＪＩＳ Ｋ−５４００）４５°１０°
拡散反射率
（２）光沢（ガラス板）：
作成した塗料を１日放置後、ガラス板
に３ミルアプリケーターにて塗布し２
０°０１６０％ＲＨ中にて５日乾燥後、村上式光沢針に
て測定した。(Test conditions) 5l- (1) Hiding rate: Apply to concealing test paper (manufactured by Japan Test Panel Industry Co., Ltd.) with a 6 mil applicator, and after drying for 5 days in 20°, 160% RH, Murakami gloss. The gloss at 45° and 10° was measured for the black and white areas of the test paper, and the ratio was calculated using the formula below. (JIS K-5400) 45°10°
Diffuse reflectance (2) Gloss (glass plate): After leaving the prepared paint for one day, apply it to the glass plate with a 3 mil applicator, dry it for 5 days in 20°, 160% RH, and apply it using a Murakami gloss needle. It was measured using
（３）耐水性；
（２）にて作成したガラス板塗膜を１
日乾燥後、室温で水に１４日間浸漬し、目視て判定した
。(3) Water resistance; After drying the glass plate coating film prepared in (2) for one day, it was immersed in water at room temperature for 14 days, and visually determined.
（４）付着性：（密着性）
作成した塗料をフレキシブル板へ刷毛
にて２回塗り（２００ｙ ／ｍ２）を行ない、５日間乾
燥後、カミソリで２ ｍｎ＋角のゴバン目を作り、セロ
ハンテープで
剥離テストを行なった。（ＪＩＳＡ−
（５）フィルム強度；
５日間乾燥した０、５ｍｍの塗膜をダンベル２号で打ち
抜き、オートグラフで
評価した。（２０°Ｃ１６０％ＲＨ）
実施例１〜１０までは、優れた隠ぺい性、光沢、密着性
、耐水性、強度を示す。例えば中空でないポリマー粒子
を使用し重合した比較例、６．７に比較し、比較になら
ない程の優れた隠ぺい性、光沢を示し、又、プラスチッ
クピグメント、市販の中空微粒子（Ｄ−１） 、試作の
中空微粒子（第１の中空微粒子（Ａ−１））単味のもの
を比較しても、比較例８〜ＩＯによって明らかなように
、かなり優れた隠ぺい性、光沢、密着性、耐水性を示し
Ｉこ。(4) Adhesion: (Adhesion) Apply the prepared paint to a flexible board twice (200y/m2) with a brush, and after drying for 5 days, make a 2mm+ square square stitch with a razor and tape it with cellophane tape. A peel test was conducted. (JISA- (5) Film strength; A coating film of 0.5 mm that had been dried for 5 days was punched out using a dumbbell No. 2 and evaluated using an autograph. (20°C, 160% RH) Examples 1 to 10 showed excellent concealment. For example, compared to Comparative Example 6.7, which was polymerized using solid polymer particles, it showed incomparably excellent hiding power and gloss, and Even when comparing single plastic pigments, commercially available hollow particles (D-1), and prototype hollow particles (first hollow particles (A-1)), as is clear from Comparative Examples 8 to IO, It exhibits excellent concealment, gloss, adhesion, and water resistance.
特に実施例１〜５、および７〜ＩＯの中空微粒子は隠ぺ
い性、光沢、耐水性等が一段と優れ、特に好ましいもの
であり、特筆すべきものである。In particular, the hollow fine particles of Examples 1 to 5 and 7 to IO are particularly preferable and worthy of special mention because they have superior hiding properties, gloss, water resistance, and the like.
比較例１は、単量体混合物（Ｂ）中のカルボン酸モノマ
ー量が８０重量部を越える量を使用しており、特に重合
安定性が悪く、新粒子の発生があり隠ぺい性、光沢、耐
水性、密着性、フィルム強度が著しく劣る。In Comparative Example 1, the amount of carboxylic acid monomer in the monomer mixture (B) exceeds 80 parts by weight, and the polymerization stability is particularly poor, and new particles are generated, resulting in poor hiding performance, gloss, and water resistance. The properties, adhesion, and film strength are significantly poor.
比較例２．３は、得られた水性分散体の粒子径が０．１
〜２０μｍをはずれる例であり、隠ぺい性、光沢、付着
性が著しく劣り、重合安定性も悪く、新粒子も発生し、
好ましくない。In Comparative Example 2.3, the particle size of the obtained aqueous dispersion was 0.1
This is an example in which the particle diameter exceeds ~20 μm, and the hiding power, gloss, and adhesion are extremely poor, the polymerization stability is also poor, and new particles are generated.
Undesirable.
比較例４は、重合時の乳化剤及び／又は分散剤を、第１
の中空微粒子（Ａ）と単量体混合物（Ｂ）の合計重量１
００重量部あたり５重量部を越える量を使用した例であ
り、内孔を有さない新粒子が多くでき、従って隠ぺい性
、光沢、が極めて劣り好ましくない。比較例５は、得ら
れた中空微粒子の粒子径か大きい例であり、重合安定性
、重合中の新粒子が発生し、目的とする隠ぺい性、光沢
をはじめとする各種の物性が劣る。In Comparative Example 4, the emulsifier and/or dispersant during polymerization was
Total weight of hollow fine particles (A) and monomer mixture (B) 1
This is an example in which an amount exceeding 5 parts by weight per 00 parts by weight is used, which is not preferable because many new particles having no inner pores are formed, and therefore the hiding power and gloss are extremely poor. Comparative Example 5 is an example in which the particle size of the obtained hollow fine particles is large, and the polymerization stability and new particles are generated during polymerization, and various physical properties such as the desired hiding power and gloss are inferior.
本発明方法で得られた中空微粒子は水性分散体の形とな
っており、このままでも使用できるし、又、乾燥し、粉
体としても使用できる。特に溶剤系塗料等の場合は、粉
体の方が好ましく、以下の方法で得られる。The hollow fine particles obtained by the method of the present invention are in the form of an aqueous dispersion, and can be used as they are, or can be dried and used as a powder. Particularly in the case of solvent-based paints, powder is preferable and can be obtained by the following method.
ＳＴ； スチレン
ＭＭＡ、 メタクリル酸メチル
ＢＡ、 アクリル酸ブチル
ＭＡＡ、 メタクリル酸
ＡＡ、 アクリル酸
ＶＰ： １１〜ビニルピリジン
ＤＶＤ 、 ジヒニルベンゼン
ＥＤＭＡ ： エチレングリコールジメタクリレート
ＺＥＨＡ、 アクリル酸２−エチルへキシルアクリエ
ステルＨＨ。ST: Styrene MMA, methyl methacrylate BA, butyl acrylate MAA, methacrylic acid AA, acrylic acid VP: 11-vinylpyridine DVD, dihinylbenzene EDMA: ethylene glycol dimethacrylate ZEHA, 2-ethylhexylacrylate acrylate HH.
ＯＯＨ
（乾燥方法）
前記実施例１の水性分散体（固形分４２％）５ｋｇを噴
霧乾燥装置（小型研究開発用モービル・マイナー型、ア
シザワニロアトマイザー（株）社製）を用いて、入口温
度１３０〜１８０°０１滴下速度１ 、５ ｋｇ／ ｈ
ｒで粒末２ 、１ ｋｇを約３．５時間で得た。OOH (Drying method) 5 kg of the aqueous dispersion (solid content 42%) of Example 1 was dried using a spray dryer (Mobil Minor type for small research and development, manufactured by Ashizawa Waniro Atomizer Co., Ltd.) at an inlet temperature of 130 ~180°01 Dripping speed 1,5 kg/h
2.1 kg of powder was obtained in about 3.5 hours.
実施例３及び５についても同様の方法で粉末化を実施し
た結果を第三表に示す。Examples 3 and 5 were also powdered using the same method, and the results are shown in Table 3.
第三表
〈発明の効果〉
本発明によれば、中空微粒子を水性媒体中において重合
を行なう簡易なプロセスによって、重合して安定性良く
、かつ工業的に製造でき、今まで不可能であった隠ぺい
性、光沢、密着性、塗膜強度を飛躍的に向上させる中空
微粒子のｉ遣方法が提供される。Table 3 <Effects of the Invention> According to the present invention, hollow fine particles can be polymerized and produced industrially with good stability through a simple process of polymerizing them in an aqueous medium, which has not been possible until now. Provided is a method for using hollow fine particles that dramatically improves hiding properties, gloss, adhesion, and coating strength.
本発明の中空微粒子は、前記した特異な光学性能を持ち
、隠ぺい性、光沢、密着性、塗膜強度が優れていること
により、主に、高隠ぺい性、軽量、等を利用して、ピグ
メント等として用いられる。The hollow fine particles of the present invention have the above-mentioned unique optical performance and are excellent in hiding properties, gloss, adhesion, and coating strength. It is used as such.
例えば塗料、紙塗工用、インキ、カーペット用、紙用内
添剤などに広く利用でき、通常の中空粒子では発現しえ
なかった前記の特徴によって、有用なものである。For example, they can be widely used in paints, paper coatings, inks, carpets, internal additives for paper, etc., and are useful because of the above-mentioned characteristics that ordinary hollow particles cannot exhibit.
又、カプセル機能の特徴を生かし、内部に溶剤、可塑剤
、香料、インク、農薬、医薬等の物質を含有することが
できるだけでなく、中空ポリマー粒子表面を自由に変性
できるメリットを有する。そのため、現在は、市販の中
空ポリマー粒子の接着性、などの改質技術がなく、はと
んど応用されていない本発明により、より具体的に上記
の用途および／又は、種々の用途分野に検討されて応用
できる。In addition, by taking advantage of the capsule function, it is possible not only to contain substances such as solvents, plasticizers, fragrances, inks, agricultural chemicals, and medicines, but also to have the advantage of being able to freely modify the surface of the hollow polymer particles. Therefore, at present, there is no technology for modifying the adhesion of commercially available hollow polymer particles, and the present invention has hardly been applied. Can be considered and applied.
ほか１名1 other person
Claims (1)
第１の中空ポリマー微粒子、 および （Ｂ）重合性不飽和カルボン酸０〜８０重量％と他の共
重合可能なモノマー２０〜１００重量％からなるモノマ
ー又はモノマー混合物を （Ｃ）上記第１の中空ポリマー微粒子（Ａ）とモノマー
又はモノマー混合物（Ｂ）の合計重量１００重量部当り
５重量以下の乳化剤 及び／又は分散剤 の存在下、水性媒体中で重合に付し、該第１の中空ポリ
マー微粒子（Ａ）の表面に該モノマー又はモノマー混合
物（Ｂ）の重合体被膜を生成せしめて平均粒径が０．１
〜２０μｍの範囲にある第２の中空ポリマー微粒子を形
成することを特徴とする中空ポリマー微粒子の製造法。 ２、第１の中空ポリマー微粒子（Ａ）の該ポリマーが （ａ）親水性の非架橋性モノマー２０〜９９重量％、架
橋性モノマー１〜８０重量％および これらのモノマーと共重合可能な他のモノマー０〜７０
重量％からなるモノマー成分の共重合体、および （ｂ）上記共重合体とは異なる重合体から成り、そして （ｃ）上記共重合体（ａ）１００重量部に対し、上記重
合体（ｂ）１〜１００重量部の組成、を有する、 特許請求の範囲第１項に記載の方法。 ３、上記親水性の非架橋性モノマーが不飽和カルボン酸
および／またはそれ以外の親水性モノマーである特許請
求の範囲第２項に記載の方法。 ４、上記親水性の非架橋性モノマーが不飽和カルボン酸
１〜７０重量％とそれ以外の親水性モノマー３０〜９９
重量％からなる特許請求の範囲第２項に記載の方法。 ５、（１）（ａ）親水性の非架橋性モノマー２０〜９９
重量％、架橋性モノマー１〜８０重量％およびこれらの
モノマーと共重合可能な他のモノマー０〜７０重量％か
らなるモノマー成分を、 （ｂ）上記モノマー成分から得られる共重合体と異なる
種となるポリマー微粒子 の存在下、該モノマー成分１００重量部当り該ポリマー
微粒子１〜１００重量部の割合で存在せしめて、水性媒
体中で重合に付して平均粒径が０．０５〜１５μｍの範
囲にある第１の中空ポリマー微粒子を形成せしめ、 次いで （２）（Ａ）上記第１の中空ポリマー微粒子、および （Ｂ）重合性不飽和カルボン酸が０．５〜５０重量％及
び他の共重合可能なモノマー５０〜９９．５重量％から
なるモノマー又はモノマー混合物を、 （Ｃ）上記第１の中空ポリマー微粒子（Ａ）とモノマー
又はモノマー混合物（Ｂ）の合計重量１００重量部当り
５重量以下の乳化剤及び／または分散剤 の存在下、水性媒体中、ｐＨ値が７より小さい条件下で
乳化重合に付し、該第１の中空ポリマー微粒子（Ａ）の
表面に該モノマー又はモノマー混合物（Ｂ）の重合体被
膜を生成せしめて平均粒径が０．１〜２０μｍの範囲に
ある第２の中空ポリマー微粒子を形成することを特徴と
する中空ポリマー微粒子の製造法。[Claims] 1. (A) first hollow polymer fine particles having an average particle size in the range of 0.05 to 15 μm; and (B) 0 to 80% by weight of a polymerizable unsaturated carboxylic acid and other co-organisms; A monomer or a monomer mixture consisting of 20 to 100% by weight of a polymerizable monomer, (C) an emulsifier of 5 weight or less per 100 parts by weight of the total weight of the first hollow polymer particles (A) and the monomer or monomer mixture (B); Polymerization is performed in an aqueous medium in the presence of/or a dispersant to form a polymer film of the monomer or monomer mixture (B) on the surface of the first hollow polymer fine particles (A), so that the average particle size is 0.1
A method for producing hollow polymer particles, the method comprising forming second hollow polymer particles having a diameter in the range of ~20 μm. 2. The polymer of the first hollow polymer fine particles (A) contains (a) 20 to 99% by weight of a hydrophilic non-crosslinkable monomer, 1 to 80% by weight of a crosslinkable monomer, and other copolymerizable monomers. Monomer 0-70
(b) a polymer different from the above copolymer, and (c) the above copolymer (b) for 100 parts by weight of the above copolymer (a); 1 to 100 parts by weight. 3. The method according to claim 2, wherein the hydrophilic non-crosslinking monomer is an unsaturated carboxylic acid and/or another hydrophilic monomer. 4. The above hydrophilic non-crosslinking monomer contains 1 to 70% by weight of unsaturated carboxylic acid and 30 to 99% of other hydrophilic monomers.
% by weight. 5, (1) (a) Hydrophilic non-crosslinking monomer 20-99
(b) a species different from the copolymer obtained from the above monomer components; In the presence of fine polymer particles, the polymer particles are present in a ratio of 1 to 100 parts by weight per 100 parts by weight of the monomer component, and the polymer particles are polymerized in an aqueous medium to have an average particle size in the range of 0.05 to 15 μm. forming certain first hollow polymer fine particles, and then (2) containing (A) the first hollow polymer fine particles and (B) 0.5 to 50% by weight of a polymerizable unsaturated carboxylic acid and other copolymerizable (C) 5 parts by weight or less of an emulsifier per 100 parts by weight of the total weight of the first hollow polymer particles (A) and the monomer or monomer mixture (B); and/or in the presence of a dispersant in an aqueous medium at a pH value of less than 7, and the monomer or monomer mixture (B) is applied to the surface of the first hollow polymer fine particles (A). A method for producing hollow polymer fine particles, which comprises forming a second hollow polymer fine particle having an average particle size in the range of 0.1 to 20 μm by forming a polymer coating.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63044282A JP2646620B2 (en) | 1988-02-29 | 1988-02-29 | Method for producing hollow polymer particles |
| CA000591870A CA1303437C (en) | 1988-02-29 | 1989-02-23 | Hollow polymer particles, process for production thereof, and use thereof as pigment |
| US07/314,929 US4972000A (en) | 1988-02-29 | 1989-02-24 | Hollow polymer particles, process for production thereof, and use thereof as pigment |
| EP89301962A EP0331421A3 (en) | 1988-02-29 | 1989-02-28 | Hollow polymer particles, process for production thereof, and use thereof as pigment |
| KR1019890002419A KR890013100A (en) | 1988-02-29 | 1989-02-28 | Hollow polymer particles, preparation method thereof and use as pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63044282A JP2646620B2 (en) | 1988-02-29 | 1988-02-29 | Method for producing hollow polymer particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01218629A true JPH01218629A (en) | 1989-08-31 |
| JP2646620B2 JP2646620B2 (en) | 1997-08-27 |
Family
ID=12687153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63044282A Expired - Lifetime JP2646620B2 (en) | 1988-02-29 | 1988-02-29 | Method for producing hollow polymer particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2646620B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088624A (en) * | 2006-10-03 | 2008-04-17 | Rohm & Haas Co | Paper or paperboard article coated with hollow organic pigment core binder and method for producing the same |
| JP2009035672A (en) * | 2007-08-03 | 2009-02-19 | Jsr Corp | Hollow particle for white ink for inkjet, method for producing the same and white ink for inkjet |
| JP2009540047A (en) * | 2006-06-08 | 2009-11-19 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Microsphere |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6019033A (en) * | 1983-07-12 | 1985-01-31 | Matsumoto Yushi Seiyaku Kk | Hollow micro-balloon and preparation thereof |
| JPS62127336A (en) * | 1985-11-28 | 1987-06-09 | Japan Synthetic Rubber Co Ltd | Polymer particle having internal hole and its production |
-
1988
- 1988-02-29 JP JP63044282A patent/JP2646620B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6019033A (en) * | 1983-07-12 | 1985-01-31 | Matsumoto Yushi Seiyaku Kk | Hollow micro-balloon and preparation thereof |
| JPS62127336A (en) * | 1985-11-28 | 1987-06-09 | Japan Synthetic Rubber Co Ltd | Polymer particle having internal hole and its production |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009540047A (en) * | 2006-06-08 | 2009-11-19 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Microsphere |
| JP2008088624A (en) * | 2006-10-03 | 2008-04-17 | Rohm & Haas Co | Paper or paperboard article coated with hollow organic pigment core binder and method for producing the same |
| JP2009035672A (en) * | 2007-08-03 | 2009-02-19 | Jsr Corp | Hollow particle for white ink for inkjet, method for producing the same and white ink for inkjet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2646620B2 (en) | 1997-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4972000A (en) | Hollow polymer particles, process for production thereof, and use thereof as pigment | |
| CA1339325C (en) | Stable emulsion polymers and methods of preparing same | |
| US6258888B1 (en) | Aqueous polymer emulsions | |
| FI95585B (en) | Polymer particles and their preparation | |
| JP2774145B2 (en) | Method for producing multilayer opaque polymer particles and coating composition containing the particles | |
| US5081166A (en) | Process for producing a stabilized latex emulsion adhesive | |
| JPH0468324B2 (en) | ||
| JPS6334884B2 (en) | ||
| EP0451940A2 (en) | Preparation of polymeric particles | |
| JPH0627123B2 (en) | Aqueous dispersion | |
| JPH07144126A (en) | Microcapsule, preparation thereof and method for releasing substance under control | |
| BRPI0805352A2 (en) | core-shell polymer particle, composition, and method for providing opacity to a dry composition | |
| EP1098927A1 (en) | Preparation of core-shell polymer particles containing voids | |
| CA2283480A1 (en) | A method for the preparation of hollow polymer particle latex | |
| JPH05125127A (en) | Polymer granule having single inner pore | |
| WO1993023437A1 (en) | Fine bowl-shaped particle and production thereof | |
| US4515914A (en) | Crosslinked latexes encapsulated with linear polymers | |
| JP2017119843A (en) | Hollow polymer particle, manufacturing method of polymer particle dispersion and manufacturing method of hollow polymer particle | |
| JPH04145131A (en) | Production of hollow polymer particle | |
| JPH02140272A (en) | Crosslinked hollow polymer pigment and coating composition using the pigment | |
| JPH0735448B2 (en) | Crosslinked hollow polymer particles | |
| JPH01218629A (en) | Method for producing hollow polymer particles | |
| JP3465826B2 (en) | Method for producing hollow polymer fine particles | |
| JPH02140271A (en) | Hollow polymer pigment and coating composition using the pigment | |
| US5246981A (en) | Aqueous emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |