JPH01146907A - Polymer emulsion and its preparation - Google Patents
Polymer emulsion and its preparationInfo
- Publication number
- JPH01146907A JPH01146907A JP30446087A JP30446087A JPH01146907A JP H01146907 A JPH01146907 A JP H01146907A JP 30446087 A JP30446087 A JP 30446087A JP 30446087 A JP30446087 A JP 30446087A JP H01146907 A JPH01146907 A JP H01146907A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- latex
- seed
- general formula
- tables
- 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
- 239000000839 emulsion Substances 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 229920000126 latex Polymers 0.000 claims abstract description 39
- 239000004816 latex Substances 0.000 claims abstract description 39
- 125000002091 cationic group Chemical group 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 9
- 239000000057 synthetic resin Substances 0.000 claims abstract description 9
- 229920006174 synthetic rubber latex Polymers 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract 4
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 9
- 238000012644 addition polymerization Methods 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000000084 colloidal system Substances 0.000 abstract description 6
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract 2
- 150000003863 ammonium salts Chemical class 0.000 abstract 2
- 239000003999 initiator Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 6
- 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 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 etc. Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229950003937 tolonium Drugs 0.000 description 2
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- 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 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
- HPGIOSOCXHTQGW-UHFFFAOYSA-N 2-(dipropylamino)ethyl prop-2-enoate Chemical compound CCCN(CCC)CCOC(=O)C=C HPGIOSOCXHTQGW-UHFFFAOYSA-N 0.000 description 1
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FKAJZOZTZXQGTJ-UHFFFAOYSA-N 5,5-dimethyl-1,3-diazabicyclo[2.2.0]hex-3-ene Chemical compound C1N2C(C1(C)C)=NC2 FKAJZOZTZXQGTJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 101100450563 Mus musculus Serpind1 gene Proteins 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- KLIYQWXIWMRMGR-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate Chemical compound C=CC=C.COC(=O)C(C)=C KLIYQWXIWMRMGR-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000004925 denaturation Methods 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- VNLHOYZHPQDOMS-UHFFFAOYSA-N n-[3-(diethylamino)propyl]-2-methylprop-2-enamide Chemical compound CCN(CC)CCCNC(=O)C(C)=C VNLHOYZHPQDOMS-UHFFFAOYSA-N 0.000 description 1
- PTQOQKRUWKRZTR-UHFFFAOYSA-N n-[3-(dipropylamino)propyl]-2-methylprop-2-enamide Chemical compound CCCN(CCC)CCCNC(=O)C(C)=C PTQOQKRUWKRZTR-UHFFFAOYSA-N 0.000 description 1
- AWWDNSVVAMLXJS-UHFFFAOYSA-N n-[3-(dipropylamino)propyl]prop-2-enamide Chemical compound CCCN(CCC)CCCNC(=O)C=C AWWDNSVVAMLXJS-UHFFFAOYSA-N 0.000 description 1
- UXJXCZLHRLBCLF-UHFFFAOYSA-N n-ethylethanamine;ethyl 2-methylprop-2-enoate Chemical compound CCNCC.CCOC(=O)C(C)=C UXJXCZLHRLBCLF-UHFFFAOYSA-N 0.000 description 1
- BVOJAXMUGDFZDX-UHFFFAOYSA-N n-ethylethanamine;ethyl prop-2-enoate Chemical compound CCNCC.CCOC(=O)C=C BVOJAXMUGDFZDX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- WZAPMUSQALINQD-UHFFFAOYSA-M potassium;ethenyl sulfate Chemical compound [K+].[O-]S(=O)(=O)OC=C WZAPMUSQALINQD-UHFFFAOYSA-M 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、カチオン性基が少なくともラテックス粒子表
面に高密度に分布し得る安定な重合体エマルジョン及び
その製造方法に関し、カチオン性を付与することにより
特に、パルプ、合成繊維。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a stable polymer emulsion in which cationic groups can be densely distributed at least on the surface of latex particles, and a method for producing the same, and particularly to a method for producing the same by imparting cationic properties. , pulp and synthetic fibers.
無機繊維抄造時のビータ−サイズ加工における紙力増強
バインダー又は定着剤、歩留向上剤など、また、植毛、
不織布、カーペットバッキング等の(以下余白)
バインダー、繊維の風合加工、帯電防止加工、防水加工
剤など、またモルタル、セメント混和剤、アスファルト
混和剤、その他接着剤、塗料原料として好適に使用され
る重合体エマルジョン及びその製造方法に関するもので
ある。Paper strength increasing binder or fixing agent, retention improver, etc. in beater size processing during inorganic fiber papermaking, flocking,
Suitable for use as a binder for nonwoven fabrics, carpet backings, etc., texture processing of fibers, antistatic processing, waterproofing agents, etc., as well as mortar, cement admixtures, asphalt admixtures, other adhesives, and raw materials for paints. This invention relates to a polymer emulsion and a method for producing the same.
従来の技術
従来からカルボキシル変性ラテックスは、たとえば各種
m維、アスファルト、モルタル、コンクリートまたはセ
ラミックなどのバインダーなどに用いられている。BACKGROUND OF THE INVENTION Carboxyl-modified latexes have been used in the past as binders for various types of fibers, asphalt, mortar, concrete, ceramics, and the like.
又、カチオン性重合体エマルジョンもいろいろ提案され
ているが、その使用目的に対し、十分な効果の得られる
ものは少なく、又その製造方法も複雑である。In addition, various cationic polymer emulsions have been proposed, but few of them are sufficiently effective for their intended use, and their production methods are also complicated.
たとえば、乳化剤を使用せず、またはカチオン性界面活
性剤を用いてシード重合により、カチオン性単量体を他
の単量体と共重合する方法がある。これは全量のカチオ
ン性単量体と他の単量体の一部を用いて種ラテックスを
作り、これに残りの単量体を添加する方法であるので、
粒子表面にカチオン性基を多数存在させることができず
、安定な重合ができない(特開昭57−121048号
公報、特開昭59−142217号公報)。For example, there is a method of copolymerizing a cationic monomer with another monomer by seed polymerization without using an emulsifier or using a cationic surfactant. This is a method in which a seed latex is made using the entire amount of cationic monomer and a portion of other monomers, and the remaining monomers are added to this.
A large number of cationic groups cannot be present on the particle surface, and stable polymerization cannot be performed (JP-A-57-121048, JP-A-59-142217).
また、第2級、第3級アミン、又は第4級アンモニウム
塩からなるカチオン性基付与剤を含有するエチレン性不
飽和単量体と、これらと共重合可能なエチレン性不飽和
単量体の一部を水性媒体中連鎖移動剤の存在下重合して
種ラテックスとし、次いで残りの単量体を添加して重合
を継続する方法がある(0開昭81−281302号)
。In addition, ethylenically unsaturated monomers containing a cationic group-giving agent consisting of a secondary, tertiary amine, or quaternary ammonium salt, and ethylenically unsaturated monomers copolymerizable with these There is a method in which a part of the monomer is polymerized in the presence of a chain transfer agent in an aqueous medium to form a seed latex, and then the remaining monomer is added to continue the polymerization (No. 081-281302).
.
この方法は、前者のものと異なり、種ラテックスに添加
する単量体にカチオン性基付与剤を含有させたものを用
いるので、成る程度粒子表面にカチオン性基を付与する
効果は期待できるが、連鎖移動剤存在下で種ラテックス
を製造するなど製造工程が複雑である。Unlike the former method, this method uses a monomer added to the seed latex that contains a cationic group imparting agent, so it can be expected to have the effect of imparting a cationic group to the particle surface to some extent; The manufacturing process is complicated, as the seed latex is manufactured in the presence of a chain transfer agent.
発明が解決しようとする問題点
本発明は公知のカルボキシル変性ラテックスを種とし、
水に対して難溶性または不溶性単量体を使用して重合中
にカチオン解離が少なく、製造法が簡単でより安定なシ
ード重合が出来、かつ重合体が酸または塩で中和、又は
4級化剤で4級アンモニウム塩化することによりラテッ
クス粒子表面に高密度にカチオン性を付与し得る重合体
ラテックスを提供するものである。Problems to be Solved by the Invention The present invention is based on a known carboxyl-modified latex,
By using monomers that are poorly soluble or insoluble in water, there is less cation dissociation during polymerization, and the production method is simple and more stable seed polymerization is possible, and the polymer is neutralized with acid or salt, or quaternary polymerization is possible. The object of the present invention is to provide a polymer latex which can impart cationic properties to the surface of latex particles at high density by converting it into a quaternary ammonium salt with a curing agent.
問題点を解決するための手段
本発明者らは、公知の合成ゴム系ラテックスまたは合成
樹脂系エマルジョンを種ラテックスとし、これに特定の
単量体をシード重合して得られたものを、酸又は塩で中
和、又は4級化剤で4級アンモニウム塩化することによ
り、カチオン性基を重合体粒子表面に高密度に存在させ
得るものが得られ、しかもエマルジョンの粒子が安定で
あり、またその製造法も簡単で複雑な操作を必要とせず
、経済的にも有利であることを見い出し、本発明に到達
したものである。Means for Solving the Problems The present inventors used a known synthetic rubber latex or synthetic resin emulsion as a seed latex, and seed latex with a specific monomer. By neutralizing with a salt or converting to a quaternary ammonium salt with a quaternizing agent, it is possible to have cationic groups present in a high density on the surface of the polymer particles, and the particles of the emulsion are stable. The present invention was achieved based on the discovery that the manufacturing method is simple, does not require complicated operations, and is economically advantageous.
すなわち、本発明は1合成ゴムラテックスまたは合成樹
脂系エマルジョンを種ラテックスとし。That is, in the present invention, a synthetic rubber latex or a synthetic resin emulsion is used as a seed latex.
これに下記、一般式〔I〕で示される単量体、又はこれ
らと共重合可能なエチレン性不飽和単量体との混合物を
添加重合して得られるシード重合体エマルジョン及び、
これを酸または塩で中和、または一般の4級化剤で4級
アンモニウム塩化することにより、ラテックス表面に高
密度にカチオン性を付与したことを特徴とする重合体エ
マルジョン、及びそれらの製造方法である。A seed polymer emulsion obtained by adding and polymerizing a monomer represented by the following general formula [I] or a mixture with an ethylenically unsaturated monomer copolymerizable with these, and
A polymer emulsion characterized by imparting cationic properties to the latex surface at high density by neutralizing it with an acid or salt or converting it into a quaternary ammonium salt with a general quaternizing agent, and a method for producing the same. It is.
\
亀
(t、だし、式中のR3はHまたはCH3,R,は炭素
数2〜5のフルキレン基、亀及び亀はHまたは炭素−C
−NH−を示し、R1、R3、亀は単量体が水に対し難
溶性または不溶性である範囲で選ばれる。)作用
以下、さらに本発明の詳細な説明する。\ Kame (t, dashi, R3 in the formula is H or CH3, R is a fullkylene group having 2 to 5 carbon atoms, Kame and Kame are H or carbon-C
-NH-, and R1, R3 and tome are selected within the range in which the monomer is poorly soluble or insoluble in water. ) Effect The present invention will be further explained in detail below.
本発明に用いられる合成ゴム系ラテックス、または合成
樹脂系エマルジョンとしては、公知のものがいずれも使
用することができる。しかしノニオン性のものは安定性
が悪く、またカチオン性のものは少なく、通常アニオン
性のものが好適に用いられる。Any known synthetic rubber latex or synthetic resin emulsion can be used in the present invention. However, nonionic ones have poor stability, and cationic ones are rare, and anionic ones are usually preferably used.
これらの具体例としては、合成ゴム系ラテックスでは、
スチレン・ブタジェンゴム(SBR)、メチルメタアク
リレート・ブタジェンゴム(MBR)、アクリロニトリ
ル・ブタジェンゴム(NBR)、またはこれらに他の単
量体成分(α)を含有するゴム、クロロプレンゴム(C
R)、 イソプレンゴム(IR)などをカルボキシル変
性したラテックスが挙げられ、合成樹脂系エマルジョン
ではアクリル酸エステル系、酢酸ビニル系、塩化ビニル
系、スチレン系の重合体又は共重合体、エチレン・酢酸
ビニル共重合体、エチレン・塩化ビニル共重合体などを
カルボキシル変性したエマルジョンが挙げられる。Specific examples of these include synthetic rubber latex,
Styrene-butadiene rubber (SBR), methyl methacrylate-butadiene rubber (MBR), acrylonitrile-butadiene rubber (NBR), or rubbers containing these and other monomer components (α), chloroprene rubber (C
R), carboxyl-modified latex such as isoprene rubber (IR), and synthetic resin emulsions include acrylic ester-based, vinyl acetate-based, vinyl chloride-based, styrene-based polymers or copolymers, and ethylene/vinyl acetate. Examples include emulsions obtained by carboxyl-modifying copolymers, ethylene/vinyl chloride copolymers, and the like.
次に本発明に用いられる特定の単量体としては一般式〔
I〕で表わされるものと、これら単量体と共重合回部な
エチレン性不飽和単量体(II)とがある。Next, the specific monomer used in the present invention has the general formula [
I] and ethylenically unsaturated monomer (II) which is copolymerizable with these monomers.
一般式(1)で表わされる単量体の具体例としては、た
とえば、ジエチルアミン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、ジブチルアミノエチルメタアクリレート、t−ブ
チルアミノエチル(メタ)アクリレート、ジエチルアミ
ノプロビルメタクリルアミド、ジプロピルアミノプロビ
ルメタクリルアミド、ジプロピルアミノプロビルアクリ
ルアミド、ジブチルアミノプロビルメタクリルアミド、
ジブチルアミノプロビルアクリルアミドなどが挙げられ
る。Specific examples of the monomer represented by general formula (1) include diethylamine ethyl acrylate, diethylaminoethyl methacrylate, dipropylaminoethyl acrylate, dipropylaminoethyl methacrylate, dibutylaminoethyl methacrylate, t-butyl Aminoethyl (meth)acrylate, diethylaminopropyl methacrylamide, dipropylaminopropyl methacrylamide, dipropylaminopropyl acrylamide, dibutylaminopropyl methacrylamide,
Examples include dibutylaminopropylacrylamide.
単量体〔I〕と共重合可能な他のエチレン性不飽和単量
体(II)としては、たとえばアクリル酸エステル、メ
タクリル酸エステル、アクリロニトリル、スチレン、酢
酸ビニル等の疎水性単量体又はN、N’−メチレンビス
アクリルアミド、ジアリルフタレート、ジビニルベンゼ
ン、(ポリ)エチレングリコールジ(メタ)アクリレー
ト等の架橋性単量体があげられる。Examples of other ethylenically unsaturated monomers (II) copolymerizable with monomer [I] include hydrophobic monomers such as acrylic esters, methacrylic esters, acrylonitrile, styrene, and vinyl acetate; , N'-methylenebisacrylamide, diallyl phthalate, divinylbenzene, and (poly)ethylene glycol di(meth)acrylate.
上記原料の使用量は次のとおりである。The usage amounts of the above raw materials are as follows.
種ラテックスに対する一般式〔I〕で示される単量体の
割合は5〜50重量%、好ましくは、10〜30重量%
程度である。The proportion of the monomer represented by general formula [I] to the seed latex is 5 to 50% by weight, preferably 10 to 30% by weight.
That's about it.
一般的なカルボキシル変性ラテックスのコロイド当量値
は−0,2〜−0,1鳳eq/gであるため、一般式〔
I〕で示される単量体の割合が5重量%未渦の場合、カ
チオン性基が少な過ぎて安定なカチオン性ラテックスは
得られない、50重量%超では、カチオン性基が過剰と
なり、また経済的にも不利となる。Since the colloidal equivalent value of general carboxyl-modified latex is -0.2 to -0.1 eq/g, the general formula [
When the proportion of the monomer shown in [I] is 5% by weight without swirling, there are too few cationic groups and a stable cationic latex cannot be obtained.When it exceeds 50% by weight, the cationic groups are excessive, and It is also economically disadvantageous.
なおコロイド当量値とは、次の方法で得られる値である
。Note that the colloid equivalent value is a value obtained by the following method.
ビーカーに蒸留水95waをとり、試料11000pp
溶液を5.Q加え、1%HCIIでpH=4.0とし、
約1分間攪拌する0次に、トルイジンブルー指示薬溶液
を2〜3滴加え、N /400PVSKで滴定する。滴
定速度は2−毎分とし、検水が青から赤に変色、10秒
間以上保持する時点を終点とする。Take 95 wa of distilled water in a beaker and add a sample of 11,000 pp.
Add the solution to 5. Add Q, adjust pH to 4.0 with 1% HCII,
Stir for about 1 minute. Then add 2-3 drops of toluidine blue indicator solution and titrate with N/400 PVSK. The titration rate is 2 minutes per minute, and the end point is when the sample water changes color from blue to red and remains for 10 seconds or more.
コロイド当量値(meq/g)
(ただしFはファクターである。)
単量体(II)は目的とするラテックスのガラス転移点
や物性に応じて定めればよいが、通常単量体〔I〕に対
して0−40重量%程度を使用する。Colloidal equivalent value (meq/g) (However, F is a factor.) Monomer (II) may be determined depending on the glass transition point and physical properties of the target latex, but usually monomer [I] About 0-40% by weight is used.
重合方法は種ラテックスを水で希釈するか、または希釈
せずに系のpHを6以上とし、次いで前記単量体を添加
し、ラジカル重合開始剤存在下、温度20〜80℃で攪
拌させながらシード重合する。The polymerization method involves diluting the seed latex with water or adjusting the pH of the system to 6 or higher without diluting it, then adding the monomer and stirring at a temperature of 20 to 80°C in the presence of a radical polymerization initiator. Seed polymerization.
系のpHが6未満の場合、単量体添加時あるいは重合時
にゲル化して安定なエマルジョンが得られない、また重
合温度は、常圧下にて特に限定されないが、実用上20
〜80℃、好ましくは30〜60℃である。If the pH of the system is less than 6, gelation occurs during monomer addition or polymerization, making it impossible to obtain a stable emulsion.Also, the polymerization temperature is not particularly limited under normal pressure, but in practical terms
-80°C, preferably 30-60°C.
この場合界面活性剤は特に添加する必要はないが、その
含有量が不十分なときは、常法に従って添加することも
できる。In this case, it is not necessary to specifically add a surfactant, but if the content is insufficient, it can be added according to a conventional method.
また本発明で使用されるラジカル重合開始剤としては、
通常の乳化重合に用いられるものが使用できる。In addition, the radical polymerization initiator used in the present invention includes:
Those used in ordinary emulsion polymerization can be used.
たとえば過硫酸アンモニウム、過硫酸カリウム、過酸化
水素等の無機過酸化物、アゾビスイソブチロニトリル、
2.2゛−アゾビス(2,4〜ジメチルバレロニトリル
、2.2°−アゾビス(2−アミジノプロパン)塩酸塩
、アゾビス(N、N’−ジメチレンイソブチルアミジン
)塩加塩等の脂肪族アゾ化合物類、ベンゾイルパーオキ
サイド、t−ブチルハイドロバーオギサイド、ジイソプ
ロピルベンゼンハイドロパーオキサイド、クメンハイド
ロパーオキサイド等のハイドロパーオキサイド類、前記
のパーオキサイド類と7スコルビン酸、多価金属塩、酸
性亜硫酸ナトリウム、ソジウムホルムアルデヒドスルホ
躯シレート等の還元剤を組合わせたレドックス系等が挙
げられる。For example, ammonium persulfate, potassium persulfate, inorganic peroxides such as hydrogen peroxide, azobisisobutyronitrile,
2. Aliphatic azo compounds such as 2'-azobis(2,4-dimethylvaleronitrile, 2.2'-azobis(2-amidinopropane) hydrochloride, azobis(N,N'-dimethyleneisobutyramidine) salt) hydroperoxides such as benzoyl peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, the above peroxides and 7-scorbic acid, polyvalent metal salts, acidic sodium sulfite, Examples include redox systems in combination with reducing agents such as sodium formaldehyde sulfosylate.
これらの重合開始剤の使用μとしては、単量体に対して
1.0〜5.0重量%程度、また重合方法の態様も回分
式、連続式等のいずれの方式であってもよい。The amount μ of these polymerization initiators used may be about 1.0 to 5.0% by weight based on the monomer, and the polymerization method may be either batchwise or continuous.
次いで得られたポリマーを酸又は塩で中和するか、又は
一般の4級化剤で4級アンモニウム塩化することにより
、カチオン性基がラテックス粒子表面に高密度に分布し
たカチオン性重合体エマルジョンが得られる。Then, by neutralizing the obtained polymer with an acid or salt, or converting it into a quaternary ammonium salt using a general quaternizing agent, a cationic polymer emulsion in which cationic groups are densely distributed on the latex particle surface is produced. can get.
カチオン化の方法としては、得られたシードを合体に室
温で攪拌しながら、酸、塩あるいは4級化剤を単量体〔
I〕に対して当量添加する。中和は瞬時に完了し、また
4級化は通常5分〜30分間程度で完了する。The cationization method involves combining the obtained seeds, stirring at room temperature, adding an acid, salt, or quaternizing agent to the monomer [
I] in an equivalent amount. Neutralization is completed instantly, and quaternization is usually completed in about 5 to 30 minutes.
酸としては塩酸、硫酸などの無機酸、酢酸、アジピン酸
、クエン酸、ギ酸などの有機酸等、境としては硫酸水素
ナトリウム、リン酸二水素ナトリウム等の酸性塩等、4
級化剤としては塩化メチル、塩化エチル、臭化メチル、
ヨウ化メチル等のハロゲン化アルキル、硫酸ジメチル、
硫酸ジエチル等の一般的なアルキル化剤が使用できる。Examples of acids include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, adipic acid, citric acid, and formic acid, and acid salts such as sodium hydrogen sulfate and sodium dihydrogen phosphate.
Grading agents include methyl chloride, ethyl chloride, methyl bromide,
Alkyl halides such as methyl iodide, dimethyl sulfate,
Common alkylating agents such as diethyl sulfate can be used.
又本発明においてはシード重合して得られた重合体を例
えばフィルム等に加工した後、前記と同様にカチオン化
することもできる。Further, in the present invention, the polymer obtained by seed polymerization can be processed into, for example, a film and then cationized in the same manner as described above.
本発明の重合体エマルジョンは、カチオン化することに
より、カチオン性、帯電防止性、親木性、極性親和性を
有するので、凝結剤、製紙用紙力増強バインダー、定着
剤、歩留向上剤、その他各種m維のバインダー、mix
の風合加工、帯電防止加工、防水加工、塗料、接着剤原
料、コンクリート混和、アスファルト混和などの用途に
用いられる。When the polymer emulsion of the present invention is cationized, it has cationic properties, antistatic properties, wood-philic properties, and polar affinity. Various m-fiber binders, mix
It is used for texture processing, antistatic processing, waterproofing, paint, adhesive raw material, concrete mixing, asphalt mixing, etc.
以下実施例を挙げて説明する。This will be explained below with reference to examples.
実施例1
攪拌機付きフラスコにカルボキシル変性SBRラテック
ス701.3g (pH8,3、固型分48%、アニオ
ンコロイド当量値ニー0.18meq/g)、N、N’
−メチレンビスアクリルアミド0.4g、および水15
9.7gを入れ良く攪拌しながら、ジエチルアミノエチ
ルメタアクリレ−) 37.5g (硫酸ジメチル4
級化物としてカチオンコロイド当量値: Q、51腸e
q/g)を滴下ロートを使用して滴下した後、為ガスを
吹き込みながら、1時間放置した。放置後、1%過硫酸
カリウム水溶液80gを添加し、50℃に加温して重合
させた。約2時間後に重合は完結した。Example 1 701.3 g of carboxyl-modified SBR latex (pH 8.3, solid content 48%, anionic colloid equivalent value 0.18 meq/g), N, N' in a flask with a stirrer.
- 0.4 g of methylenebisacrylamide, and 15 g of water
Add 9.7 g of diethylaminoethyl methacrylate) and add 37.5 g of dimethyl sulfate while stirring well.
Cation colloid equivalent value as graded product: Q, 51 e
q/g) was added dropwise using a dropping funnel, and then left to stand for 1 hour while blowing in gas. After standing, 80 g of a 1% potassium persulfate aqueous solution was added, and the mixture was heated to 50° C. for polymerization. Polymerization was completed after about 2 hours.
実施例2
実施例1において、N、N’−メチレンビスアクリルア
ミドを添加しない以外は、同様の操作によって安定な重
合体エマルジョンを得た。Example 2 A stable polymer emulsion was obtained in the same manner as in Example 1, except that N,N'-methylenebisacrylamide was not added.
実施例3
攪拌機付きフラスコにカルボキシル変性MBRラテック
ス530g (pH8,8、固型分45%、アニオン
コロイド当量値: −0,20meq/g)、および水
55gを入れ良く攪拌しながら、メチルメタアクリレー
ト20g、およびジエチルアミノエチルメタアクリレ−
) 40gを滴下ロートを用いて滴下した後、馬ガスを
吹き込みながら、1時間放置した。放置後、1%過硫酸
カリウム120gを加え、40℃に加温して重合させた
。約3時間後に重合は完結した。Example 3 530 g of carboxyl-modified MBR latex (pH 8.8, solid content 45%, anion colloid equivalent value: -0.20 meq/g) and 55 g of water were placed in a flask equipped with a stirrer, and while stirring well, 20 g of methyl methacrylate was added. , and diethylaminoethyl methacrylate
) After dropping 40 g using a dropping funnel, it was left for 1 hour while blowing horse gas. After standing, 120 g of 1% potassium persulfate was added, and the mixture was heated to 40°C to polymerize. Polymerization was completed after about 3 hours.
実施例4
実施例3におけるメチルメタアクリレートを酢酸ビニル
に変えた以外は同様の操作によって安定な重合体エマル
ジョンヲ得た。Example 4 A stable polymer emulsion was obtained in the same manner as in Example 3 except that vinyl acetate was used instead of methyl methacrylate.
実施例5
実施例1におけるジエチルアミノエチルメタアクリレー
トをt−ブチルアミノエチルメタアクリレートに変えた
以外は同様の操作によって安定な重合体エマルジョンを
得た。Example 5 A stable polymer emulsion was obtained in the same manner as in Example 1 except that diethylaminoethyl methacrylate was changed to t-butylaminoethyl methacrylate.
比較例1
実施例1において重合系のpHを5.8に調整した他は
同様の操作により重合を行なった所、重合開始から30
分後にゲル化した。Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the pH of the polymerization system was adjusted to 5.8.
It gelled after minutes.
比較例2
実施例1においてジエチルアミンエチルメタアクリレー
ト37.5gを13.2g (硫酸ジメチル4級化物
としてカチオンコロイド当量値: O,18meq/g
)に変えた他は同様の操作によって安定な重合体エマル
ジョンを得た。Comparative Example 2 In Example 1, 37.5 g of diethylamine ethyl methacrylate was added to 13.2 g (cation colloid equivalent value as dimethyl sulfate quaternized product: O, 18 meq/g)
) A stable polymer emulsion was obtained by the same procedure except that
比較例3
実施例1においてジエチルアミノエチルメタアクリレー
トをジメチルアミノエチルメタアクリレート(水溶性単
量体)に変えた他は同様の操作によって重合を行なった
所1重合開始直後にゲル化した。Comparative Example 3 Polymerization was carried out in the same manner as in Example 1 except that diethylaminoethyl methacrylate was changed to dimethylaminoethyl methacrylate (water-soluble monomer), and gelation occurred immediately after the start of polymerization.
以上の実施例および比較例を表−1に一覧表として示す
。The above Examples and Comparative Examples are listed in Table-1.
(以下余白)
次に、表−1の重合体エマルジョンを攪拌しながら、室
温にて単量体〔I〕に対して当量の硫酸ジメチルを添加
して30分間放置し、4級化を行なった。(Left below) Next, while stirring the polymer emulsion in Table 1, an equivalent amount of dimethyl sulfate was added to monomer [I] at room temperature, and the mixture was left to stand for 30 minutes to perform quaternization. .
カチオン化の度合は、トルイジンブルーを指示薬、!=
Lテ、 pHa、oニオはルN /400P、V、S
、に、 ニよるコロイド当量値を測定した。その結果を
表−2に示す。The degree of cationization is indicated by toluidine blue! =
Lte, pHa, oNio /400P, V, S
The colloidal equivalent value was measured by . The results are shown in Table-2.
表−2カ千オΔ生重合体エマルジョン
発明の効果
本発明は種ラテックスとして既製のポリマーラテックを
用いるので1種ラテックスを調製する手間が省け、又シ
ード重合が安定して行え、得られたエマルジョンの粒子
径も均一で、保存性も良好である。Table 2: Effects of the Invention of Kakou Δ Raw Polymer Emulsion The present invention uses a ready-made polymer latex as the seed latex, which saves the effort of preparing the first kind of latex, and allows for stable seed polymerization, resulting in the resulting emulsion. The particle size is uniform and the storage stability is good.
種ラテックスや単量体の種類の選定により、種々の特性
のものが調製できる。さらに後変性によりカチオン化さ
せるため、表面のカチオン化密度が大である。各種混和
剤や紙加工剤などの有用な用途がある。Products with various properties can be prepared by selecting the seed latex and the type of monomer. Furthermore, since the material is cationized by post-denaturation, the cationization density on the surface is high. It has useful uses such as various admixtures and paper processing agents.
Claims (5)
は合成樹脂系エマルジョンを種ラテックスとし、これに
下記一般式〔 I 〕で示される単量体、またはこれらと
共重合可能なエチレン性不飽和単量体〔II〕との混合物
を添加重合して得られるシード重合体を、酸または塩で
中和するか、または4級化剤で4級アンモニウム塩化す
ることにより、エマルジョン粒子表面に高密度にカチオ
ン性を付与したことを特徴とする重合体エマルジョン。 一般式 ▲数式、化学式、表等があります▼〔 I 〕 (ただし、式中のR_1はHまたはCH_3を、R_2
は炭素数2〜5のアルキレン基を、R_3及びR_4は
H又は炭素数1〜5のアルキル基を、Aは▲数式、化学
式、表等があります▼ま たは▲数式、化学式、表等があります▼を示し、R_1
、R_3、R_4は単量体が水に対し難溶性または不溶
性である範囲で選ばれる。)(1) A carboxyl-modified synthetic rubber latex or synthetic resin emulsion is used as a seed latex, and a monomer represented by the following general formula [I] or an ethylenically unsaturated monomer copolymerizable with these is added to the seed latex. The seed polymer obtained by addition polymerization of the mixture with [II]] is neutralized with an acid or salt, or it is converted into a quaternary ammonium salt using a quaternizing agent to impart cationic properties to the surface of the emulsion particles at a high density. A polymer emulsion characterized in that it has been added. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (However, R_1 in the formula is H or CH_3, R_2
is an alkylene group with 2 to 5 carbon atoms, R_3 and R_4 are H or an alkyl group with 1 to 5 carbon atoms, and A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲There are mathematical formulas, chemical formulas, tables, etc.▼ , R_1
, R_3, and R_4 are selected within a range in which the monomer is poorly soluble or insoluble in water. )
変性ラテックスのコロイド当量値(絶対値)以上である
特許請求の範囲第(1)項記載の重合体エマルジョン。(2) The polymer emulsion according to claim (1), wherein the amount of the monomer of general formula [I] added is at least the colloidal equivalent value (absolute value) of the carboxyl-modified latex.
合成樹脂系エマルジョンを種ラテックスとし、この種ラ
テックスを中和してpH6以上とした後、前記一般式〔
I 〕で示される単量体、またはこれと共重合可能なエ
チレン性不飽和単量体との混合物を、下記一般式〔 I
〕で示される単量体が少なくとも種ラテックスのコロイ
ド当量値(絶対値)以上の割合で添加した後、ラジカル
重合開始剤を用いて重合して得られるシード重合体に、
酸または塩を添加して中和するか、または4級化剤を添
加して4級アンモニウム塩化し、エマルジョン粒子表面
に高密度にカチオン性を付与したことを特徴とする重合
体エマルジョンの製造方法。 一般式 ▲数式、化学式、表等があります▼〔 I 〕 (ただし、式中のR_1はHまたはCH_3を、R_2
は炭素数2〜5のアルキレン基を、R_3及びR_4は
H又は炭素数1〜5のアルキル基を、Aは▲数式、化学
式、表等があります▼ま たは▲数式、化学式、表等があります▼を示し、R_1
、R_3、R_4は単量体が水に対し難溶性または不溶
性である範囲で選ばれる。)(3) A carboxyl-modified synthetic rubber latex or a synthetic resin emulsion is used as a seed latex, and after neutralizing this seed latex to a pH of 6 or more, the general formula [
A monomer represented by the following general formula [ I
] To the seed polymer obtained by adding the monomer shown in at least a proportion equal to or higher than the colloidal equivalent value (absolute value) of the seed latex, and then polymerizing it using a radical polymerization initiator,
A method for producing a polymer emulsion, characterized in that it is neutralized by adding an acid or salt, or is converted to a quaternary ammonium salt by adding a quaternizing agent, thereby imparting cationic properties to the surface of the emulsion particles at a high density. . General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (However, R_1 in the formula is H or CH_3, R_2
is an alkylene group with 2 to 5 carbon atoms, R_3 and R_4 are H or an alkyl group with 1 to 5 carbon atoms, and A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲There are mathematical formulas, chemical formulas, tables, etc.▼ , R_1
, R_3, and R_4 are selected within a range in which the monomer is poorly soluble or insoluble in water. )
は合成樹脂系エマルジョンを種ラテックスとし、これに
下記一般式〔 I 〕で示される単量体、またはこれらと
共重合可能なエチレン性不飽和単量体〔II〕との混合物
を添加重合して得られるシード重合体。 一般式 ▲数式、化学式、表等があります▼〔 I 〕 (ただし、式中のR_1はHまたはCH_3を、R_2
は炭素数2〜5のアルキレン基を、R_3及びR_4は
H又は炭素数1〜5のアルキル基を、Aは▲数式、化学
式、表等があります▼ま たは▲数式、化学式、表等があります▼を示し、R_1
、R_3、R_4は単量体が水に対し難溶性または不溶
性である範囲で選ばれる。)(4) A carboxyl-modified synthetic rubber latex or synthetic resin emulsion is used as a seed latex, and a monomer represented by the following general formula [I] or an ethylenically unsaturated monomer copolymerizable with these is added to the seed latex. Seed polymer obtained by addition polymerization of a mixture with [II]]. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (However, R_1 in the formula is H or CH_3, R_2
is an alkylene group with 2 to 5 carbon atoms, R_3 and R_4 are H or an alkyl group with 1 to 5 carbon atoms, and A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲There are mathematical formulas, chemical formulas, tables, etc.▼ , R_1
, R_3, and R_4 are selected within a range in which the monomer is poorly soluble or insoluble in water. )
合成樹脂系エマルジョンを種ラテックスとし、この種ラ
テックスを中和してpH6以上とした後、前記一般式〔
I 〕で示される単量体、またはこれと共重合可能なエ
チレン性不飽和単量体との混合物を、下記一般式〔 I
〕で示される単量体が少なくとも種ラテックスのコロイ
ド当量値(絶対値)以上の割合で添加した後、ラジカル
重合開始剤を用いて重合して得られるシード重合体の製
造方法。(5) A carboxyl-modified synthetic rubber latex or a synthetic resin emulsion is used as a seed latex, and after neutralizing this seed latex to a pH of 6 or higher, the general formula [
A monomer represented by the following general formula [ I
] A method for producing a seed polymer, which is obtained by adding the monomer represented by the following in a proportion equal to or higher than the colloidal equivalent value (absolute value) of the seed latex, and then polymerizing the mixture using a radical polymerization initiator.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62304460A JPH0762052B2 (en) | 1987-12-03 | 1987-12-03 | Polymer emulsion and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62304460A JPH0762052B2 (en) | 1987-12-03 | 1987-12-03 | Polymer emulsion and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01146907A true JPH01146907A (en) | 1989-06-08 |
JPH0762052B2 JPH0762052B2 (en) | 1995-07-05 |
Family
ID=17933284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62304460A Expired - Fee Related JPH0762052B2 (en) | 1987-12-03 | 1987-12-03 | Polymer emulsion and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0762052B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6211321B1 (en) | 1995-11-28 | 2001-04-03 | Nippon Zeon Co., Ltd. | Diene rubber |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430910A (en) * | 1977-08-10 | 1979-03-07 | Nippon Zeon Co | Paper coating composition |
JPS61275498A (en) * | 1985-05-30 | 1986-12-05 | ジェイエスアール株式会社 | Paper coating composition |
JPS62110996A (en) * | 1985-11-06 | 1987-05-22 | ジェイエスアール株式会社 | Paper coating composition for gravure printing |
-
1987
- 1987-12-03 JP JP62304460A patent/JPH0762052B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430910A (en) * | 1977-08-10 | 1979-03-07 | Nippon Zeon Co | Paper coating composition |
JPS61275498A (en) * | 1985-05-30 | 1986-12-05 | ジェイエスアール株式会社 | Paper coating composition |
JPS62110996A (en) * | 1985-11-06 | 1987-05-22 | ジェイエスアール株式会社 | Paper coating composition for gravure printing |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6211321B1 (en) | 1995-11-28 | 2001-04-03 | Nippon Zeon Co., Ltd. | Diene rubber |
Also Published As
Publication number | Publication date |
---|---|
JPH0762052B2 (en) | 1995-07-05 |
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