JPH04161403A - Production of copolymer latex - Google Patents
Production of copolymer latexInfo
- Publication number
- JPH04161403A JPH04161403A JP28941990A JP28941990A JPH04161403A JP H04161403 A JPH04161403 A JP H04161403A JP 28941990 A JP28941990 A JP 28941990A JP 28941990 A JP28941990 A JP 28941990A JP H04161403 A JPH04161403 A JP H04161403A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- polymerization
- pts
- monomer
- 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
- 239000004816 latex Substances 0.000 title claims abstract description 32
- 229920000126 latex Polymers 0.000 title claims abstract description 32
- 229920001577 copolymer Polymers 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 20
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 14
- 150000001993 dienes Chemical class 0.000 claims abstract description 8
- 150000002170 ethers Chemical class 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 17
- 239000000853 adhesive Substances 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 description 24
- -1 dimethylaminoethyl Chemical group 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000003505 polymerization initiator Substances 0.000 description 18
- 235000019645 odor Nutrition 0.000 description 16
- 239000000123 paper Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002019 disulfides Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 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
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 2
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 2
- ZUDLIFVTNPYZJH-UHFFFAOYSA-N 1,1,2,2-tetraphenylethylbenzene Chemical compound C1=CC=CC=C1C(C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 ZUDLIFVTNPYZJH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FUPIVZHYVSCYLX-UHFFFAOYSA-N 1,4-dihydronaphthalene Chemical compound C1=CC=C2CC=CCC2=C1 FUPIVZHYVSCYLX-UHFFFAOYSA-N 0.000 description 1
- DTFFFOGZHBBKCX-UHFFFAOYSA-N 2-[bis(2-aminoethyl)amino]-2-octyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)(N(CCN)CCN)CCCCCCCC DTFFFOGZHBBKCX-UHFFFAOYSA-N 0.000 description 1
- PTFSLTXIXFNFSI-UHFFFAOYSA-N 2-[bis(2-aminoethyl)amino]tetradecanoic acid Chemical class CCCCCCCCCCCCC(C(O)=O)N(CCN)CCN PTFSLTXIXFNFSI-UHFFFAOYSA-N 0.000 description 1
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- IZFHMLDRUVYBGK-UHFFFAOYSA-N 2-methylene-3-methylsuccinic acid Chemical compound OC(=O)C(C)C(=C)C(O)=O IZFHMLDRUVYBGK-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 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
- AEDQNOLIADXSBB-UHFFFAOYSA-N 3-(dodecylazaniumyl)propanoate Chemical compound CCCCCCCCCCCCNCCC(O)=O AEDQNOLIADXSBB-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 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 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical class C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-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
- 239000002253 acid Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-O carboxymethyl-[3-(dodecanoylamino)propyl]-dimethylazanium Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC(O)=O MRUAUOIMASANKQ-UHFFFAOYSA-O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 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
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 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
- 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229940094506 lauryl betaine Drugs 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
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000011087 paperboard Substances 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、接着剤等に使用したとき、接着強度や耐ブリ
スター性などの特性に優れ、かつ臭気の少ない共重合体
ラテックスの製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a copolymer latex that has excellent properties such as adhesive strength and blister resistance and has little odor when used in adhesives and the like. .
［従来の技術］ 共役ジエン系単量体、エチレン系不飽和単量体。[Conventional technology] Conjugated diene monomer, ethylenically unsaturated monomer.
エチレン系不飽和カルボン酸などからなる単量体を乳化
重合して得られる共重合体ラテックスは、接着性に優れ
ることから各種の接着剤として広く使用されている。Copolymer latex obtained by emulsion polymerization of monomers such as ethylenically unsaturated carboxylic acids is widely used as various adhesives because of its excellent adhesive properties.
これら共重合体ラテックスの製造時には、メルカプタン
化合物やジスルフィド化合物が重合連鎖移動剤として有
効であり、広く使用されている。When producing these copolymer latexes, mercaptan compounds and disulfide compounds are effective as polymerization chain transfer agents and are widely used.
しかしながら、メルカプタン化合物やジスルフィド化合
物は一般的に不快臭を有し、この臭気は重合中のみなら
ず、製品加工過程においても問題となる場合があり、こ
の臭気の軽減が望まれていた。However, mercaptan compounds and disulfide compounds generally have an unpleasant odor, and this odor may pose a problem not only during polymerization but also during product processing, and it has been desired to reduce this odor.
このため、例えば特開昭５３−１２１８９０号公報では
、臭気の少ない非イオウ系連鎖移動剤の使用が提案され
ている。しかしながら、これらの連鎖移動剤は高価であ
り、実用性において問題があった。For this reason, for example, JP-A-53-121890 proposes the use of a non-sulfur chain transfer agent with less odor. However, these chain transfer agents are expensive and have problems in practical use.
［発明が解決しようとする課題］
本発明は、接着剤等に使用したとき、接着強度、耐ブリ
スター性等の特性に優れ、かつ実質的に臭気のない共重
合体ラテックスの製造方法を提供することを目的とする
ものである。[Problems to be Solved by the Invention] The present invention provides a method for producing a copolymer latex that has excellent properties such as adhesive strength and blister resistance when used in adhesives, etc., and is substantially odorless. The purpose is to
［課題を解決するための手段］
本発明者らは、鋭意検討の結果、単量体を特定の有機溶
剤の存在下に乳化重合して得られる共重合体ラテッツク
スを用いることにより、上記目的を達成することを見い
出し、この知見に基づいて本発明を完成するに至った。[Means for Solving the Problem] As a result of intensive studies, the present inventors have achieved the above object by using a copolymer latex obtained by emulsion polymerization of monomers in the presence of a specific organic solvent. The present invention was completed based on this finding.
すなわち、本発明は、
（ａ）共役ジエン系単量体 １０〜８０重量部（ｂ）
エチレン系不飽和単量体
２０〜９０重量部
を含む単量体１００重量部を乳化重合するに際して、
重合連鎖移動剤０，１〜１０重量部と、水溶性のエーテ
ル類および／またはモノアルコール類０．５〜２０重量
部（以下、総称して「有機溶剤」という）と、
の存在下で乳化重合することを特徴とする共重合体ラテ
ックスの製造方法を提供するものである。That is, the present invention includes (a) 10 to 80 parts by weight of a conjugated diene monomer (b)
When emulsion polymerizing 100 parts by weight of monomers containing 20 to 90 parts by weight of ethylenically unsaturated monomers, 0.1 to 10 parts by weight of a polymerization chain transfer agent and water-soluble ethers and/or monoalcohols are added. The present invention provides a method for producing a copolymer latex, characterized in that emulsion polymerization is carried out in the presence of 0.5 to 20 parts by weight (hereinafter collectively referred to as "organic solvent").
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において使用される単量体は、以下に示す単量体
成分（ａ）および（ｂ）を含む。The monomers used in the present invention include monomer components (a) and (b) shown below.
（ａ）共役ジエン系単量体
共役ジエン系単量体の具体例としては、ブタジェン、イ
ソプレン、２−クロル−１，３−ブタジェン、２−メチ
ル−１，３−ブタジェンなどを挙げることができる。こ
れらは、単独で、あるいは２種以上を組み合わせて使用
することができる。(a) Conjugated diene monomer Specific examples of the conjugated diene monomer include butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene, etc. . These can be used alone or in combination of two or more.
これらのうち、特にブタジェンが好ましい。Among these, butadiene is particularly preferred.
共役ジエン系単量体の使用量は、全単量体１００重量部
に対し１０〜８０重量部、好ましくは１０〜７０重量部
、特に好ましくは２０〜６５重量部の範囲から選ばれる
。この使用量が１０重量部未満ては十分な接着強度を得
ることができず、一方８０重量部を越えると耐水性およ
び接着強度が低下して好ましくない。The amount of the conjugated diene monomer to be used is selected from the range of 10 to 80 parts by weight, preferably 10 to 70 parts by weight, particularly preferably 20 to 65 parts by weight, based on 100 parts by weight of the total monomers. If the amount used is less than 10 parts by weight, sufficient adhesive strength cannot be obtained, while if it exceeds 80 parts by weight, water resistance and adhesive strength will decrease, which is not preferred.
（ｂ）エチレン系不飽和単量体
このエチレン系不飽和単量体の具体例としては、スチレ
ン、α−メチルスチレン、ビニルトルエン、ｐ−メチル
スチレンなどの芳香族ビニル化合物；（メタ）アクリル
酸メチル、（メタ）アクリル酸エチル、（メタ）アクリ
ル酸ブチル、（メタ）アクリル酸２−ヒドロキシエチル
、（メタ）アクリル酸２−ヒドロキシエチル、メタクリ
ル酸グリシジルなどのアクリル酸またはメタクリル酸の
アルキルエステル化合物；アクリルアミド、メタクリル
アミド、Ｎ、Ｎ−ジメチルアクリルアミド、Ｎ−メチロ
ールアクリルアミドなどのエチレン系不飽和カルボン酸
のアクリルアミドまたはメタクリルアミド化合物；酢酸
ビニルなどのカルボン酸ビニルエステル類；２−シアノ
エチル（メタ）アクリレート、アクリロニトリル、メタ
クリロニトリル、α−クロルアクリロニトリルなどのシ
アン化ビニル化合物；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、２−ビニルピリジン、４−ビニルピリジン等の塩基
性単量体類；アクリル酸、メタクリル酸、クロトン酸な
どのモノカルボン酸類；マレイン酸、フマル酸、イタコ
ン酸などのジカルボン酸類；さらにマレイン酸メチル、
イタコン酸メチル、β−メタアクリルオキシエチルアシ
ッドヘキサハイドロフタレート等のハーフエステル類な
どの不飽和カルボン酸を挙げることかできる。また、ジ
カルボン酸の無水物も使用することができる。(b) Ethylenically unsaturated monomer Specific examples of this ethylenically unsaturated monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene; (meth)acrylic acid Alkyl ester compounds of acrylic acid or methacrylic acid such as methyl, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and glycidyl methacrylate. ; acrylamide or methacrylamide compounds of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide; carboxylic acid vinyl esters such as vinyl acetate; 2-cyanoethyl (meth)acrylate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; basic monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-vinylpyridine, and 4-vinylpyridine; Monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and methyl maleate,
Mention may be made of unsaturated carboxylic acids such as half esters such as methyl itaconate and β-methacryloxyethyl acid hexahydrophthalate. Anhydrides of dicarboxylic acids can also be used.
これらは単独で、あるいは２種以上を組合わせて使用す
ることができる。これらのうち、特に芳香族ビニル化合
物としてはスチレンなどが、アルキルエステル化合物と
してはメタクリル酸メチルなどが、シアン化ビニル化合
物としてはアクリロニトリルなどが、また不飽和カルボ
ン酸としてはアクリル酸、イタコン酸などが好適に使用
される。These can be used alone or in combination of two or more. Among these, aromatic vinyl compounds include styrene, alkyl ester compounds include methyl methacrylate, vinyl cyanide compounds include acrylonitrile, and unsaturated carboxylic acids include acrylic acid and itaconic acid. Preferably used.
エチレン系不飽和単量体は、得られる共重合体に適度の
硬さ、弾性および耐水性を付与するために使用するが、
その使用量は、全単量体１００重量部に対し、２０〜９
０重量部、好ましくは２０〜８０重量部の範囲から選ば
れる。この使用量が、２０重量部未満では耐水性が劣り
、一方９０重量部を越えると共重合体が硬くなりすぎ、
接着強度が低下して好ましくない。The ethylenically unsaturated monomer is used to impart appropriate hardness, elasticity, and water resistance to the resulting copolymer.
The amount used is 20 to 9 parts by weight per 100 parts by weight of the total monomers.
0 parts by weight, preferably from 20 to 80 parts by weight. If the amount used is less than 20 parts by weight, the water resistance will be poor, while if it exceeds 90 parts by weight, the copolymer will become too hard.
This is not preferable because the adhesive strength decreases.
本発明においては、（ｂ）成分の一部として不飽和カル
ボン酸単量体を全単量体１００重量部に対し通常０゜５
〜１０重量部、好ましくは１〜７重量部使用することに
より、得られる共重合体ラテックスの接着強度ならびに
機械的安定性をさらに向上させることができる。In the present invention, as part of component (b), an unsaturated carboxylic acid monomer is usually added in an amount of 0.5 parts per 100 parts by weight of the total monomers.
By using up to 10 parts by weight, preferably 1 to 7 parts by weight, the adhesive strength and mechanical stability of the resulting copolymer latex can be further improved.
次に、本発明の共重合体ラテックスの製造方法に使用さ
れる有機溶剤は、常圧における沸点（ｂ。Next, the organic solvent used in the method for producing the copolymer latex of the present invention has a boiling point (b) at normal pressure.
ｐ）が通常２５０℃以下、好ましくは３０〜２００℃で
、かつ水溶性である。p) is usually 250°C or less, preferably 30 to 200°C, and is water-soluble.
有機溶剤の沸点（ｂ、ｐ）が２５０℃を越えると、スト
リッピングや減圧蒸溜での溶剤の回収が困難となり、共
重合体ラテックス中に溶剤が残存するため好ましくない
。If the boiling point (b, p) of the organic solvent exceeds 250° C., it will be difficult to recover the solvent by stripping or vacuum distillation, and the solvent will remain in the copolymer latex, which is not preferable.
また、本発明において水溶性とは、２０℃における水に
対する溶解度が１重量％を越えることを意味する。Furthermore, in the present invention, water-soluble means that the solubility in water at 20° C. exceeds 1% by weight.
さらに、本発明の共重合体ラテックスの製造方法に使用
される有機溶剤は溶解パラメーターが７〜１４であるこ
とが好ましい。なお、溶解パラメーター６は、下記式
％式％
（Δｈ５．：モル蒸発熱＋ ｖＯ：モル体積）より求
めることができる。Further, the organic solvent used in the method for producing a copolymer latex of the present invention preferably has a solubility parameter of 7 to 14. The solubility parameter 6 can be determined from the following formula % (Δh5.: molar heat of vaporization + vO: molar volume).
有機溶剤のうちエーテル類としては、例えばテトラヒド
ロフラン（ｂ、ｐ−６６℃、δ−９，１）、ジオキサン
（ｂ 、 ｐ −１０１，３℃、δ−９，８）等が挙
げられる。Examples of ethers among organic solvents include tetrahydrofuran (b, p-66°C, δ-9,1), dioxane (b, p-101,3°C, δ-9,8), and the like.
このようなエーテル類においては、沸点は好ましくは３
４〜２００℃であり、溶解バラメーターハ好ましくは７
〜１１、より好ましくは７．２〜１０．５である。In such ethers, the boiling point is preferably 3
4 to 200°C, and the solubility parameter is preferably 7.
-11, more preferably 7.2-10.5.
また、モノアルコール類としては、例えばメタノール（
ｂ、 ｐ−６４，５，δ−１２，９） 、エタノール
（ｂ、 ｐ−７８，３℃、δ−１１，５） 、 ２
−プロパツール（ｂ 、 ｐ −８２，４，δ−１１
，５） 、 ｔｅｒｔ−ブチルアル：７−ル（ｂ、
ｐ−８２，５，６−Ｌｏ、７）等の炭素数５以下のもの
が挙げられる。In addition, examples of monoalcohols include methanol (
b, p-64,5, δ-12,9), ethanol (b, p-78,3℃, δ-11,5), 2
-Proper tool (b, p -82,4, δ-11
,5), tert-butyral:7-l (b,
Examples include those having 5 or less carbon atoms, such as p-82,5,6-Lo, 7).
このようなアルコール類においては、沸点が好ましくは
３０〜２３０℃であり、溶解パラメーターは好ましくは
７．５〜１３である。In such alcohols, the boiling point is preferably 30 to 230°C, and the solubility parameter is preferably 7.5 to 13.
これら特定の有機溶剤の使用量は全単量体１００重量部
に対して０５〜２０重量部、好ましくは０．５〜１５重
量部、さらに好ましくは１〜１０重量部である。The amount of these specific organic solvents used is 05 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total monomers.
この使用量が０．５重量部未満ては、本発明の目的であ
る重合連鎖移動剤の使用量の軽減が達成できず、得られ
る共重合体ラテックスの臭気を実質的になくすことがで
きない。一方、使用量が２０重量部を越えると、重合中
に多量の凝固物が発生し、好ましくない。If the amount used is less than 0.5 parts by weight, the reduction in the amount of polymerization chain transfer agent used, which is the object of the present invention, cannot be achieved, and the odor of the resulting copolymer latex cannot be substantially eliminated. On the other hand, if the amount used exceeds 20 parts by weight, a large amount of coagulum will be generated during polymerization, which is not preferable.
本発明においては、重合連鎖移動剤と有機溶剤とを併用
することにより、重合連鎖移動剤の使用量を相対的に低
減することができ、その結果メルカプタン化合物やジス
ルフィド化合物等による不快臭を実質的にかなりなくす
ことができる。In the present invention, by using a polymer chain transfer agent and an organic solvent together, the amount of the polymer chain transfer agent used can be relatively reduced, and as a result, unpleasant odors caused by mercaptan compounds, disulfide compounds, etc. can be substantially reduced. can be eliminated considerably.
本発明における共重合体ラテックスの製造方法は、上記
の単量体および有機溶剤を使用する点を除けば、従来公
知の乳化重合方法によって行うことがてきる。すなわち
、水性媒体（通常、水）に単量体、有機溶剤ならびに重
合開始剤、乳化剤、重合連鎖移動剤などを加えて乳化重
合を行う。The method for producing the copolymer latex in the present invention can be carried out by a conventionally known emulsion polymerization method, except that the above-mentioned monomers and organic solvents are used. That is, emulsion polymerization is carried out by adding a monomer, an organic solvent, a polymerization initiator, an emulsifier, a polymerization chain transfer agent, etc. to an aqueous medium (usually water).
本発明における乳化重合に使用する重合開始剤について
は特に制限はなく、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などのハイドロパ
ーオキサイド類、ベンゾイルパーオキサイド、ラウロイ
ルパーオキサイドなどのパーオキサイド類およびアゾビ
スイソブチロニトリルなどのアゾ化合物類などの有機系
重合開始剤、ならびに過硫酸カリウム、過硫酸ナトリウ
ム、過硫酸アンモニウムなどの過硫酸塩などの無機系重
合開始剤を使用することができる。There are no particular limitations on the polymerization initiator used in the emulsion polymerization in the present invention, such as cumene hydroperoxide, diisopropylbenzene hydroperoxide,
Hydroperoxides such as paramenthane hydroperoxide, peroxides such as benzoyl peroxide and lauroyl peroxide, and organic polymerization initiators such as azo compounds such as azobisisobutyronitrile, as well as potassium persulfate and peroxide. Inorganic polymerization initiators such as persulfates such as sodium sulfate and ammonium persulfate can be used.
本発明においては、有機系重合開始剤を単独で使用する
と得られる共重合体ラテックスの機械的安定性が劣り、
また重合中に多量の凝固物が発生することから、無機系
重合開始剤を単独で、あるいは有機系重合開始剤と組合
わせて使用するのが好ましい。In the present invention, when an organic polymerization initiator is used alone, the mechanical stability of the copolymer latex obtained is poor;
Furthermore, since a large amount of coagulated material is generated during polymerization, it is preferable to use an inorganic polymerization initiator alone or in combination with an organic polymerization initiator.
なお、上記重合開始剤は重亜硫酸ナトリウムなどの還元
剤と組合わせた、いわゆるレドックス系重合開始剤とし
ても使用することができる。The above polymerization initiator can also be used as a so-called redox polymerization initiator in combination with a reducing agent such as sodium bisulfite.
これら重合開始剤のうち、過硫酸カリウム、過硫酸アン
モニウムなどの過硫酸塩、またはこれとアゾビスイソブ
チロニトリルあるいはベンゾイルパーオキサイドとの組
合せ、さらにはこれらと還元剤とを組合わせたものが好
ましく使用される。Among these polymerization initiators, persulfates such as potassium persulfate and ammonium persulfate, combinations thereof with azobisisobutyronitrile or benzoyl peroxide, and combinations thereof with reducing agents are preferred. used.
本発明における重合開始剤の使用量は、全単量体１００
重量部当り、通常０．１〜５重量部であり、好ましくは
０５〜２重量部である。無機系重合開始剤と有機系重合
開始剤とを併用する場合には、有機系重合開始剤の割合
は、好ましくは全重合開始剤の７０重量％以下、さらに
好ましくは５０重量％以下である。有機系重合開始剤の
割合が７０重量％を越えると、有機系重合開始剤を単独
で使用した場合のような問題が生じて好ましくない。The amount of polymerization initiator used in the present invention is 100% of the total monomer.
It is usually 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight. When an inorganic polymerization initiator and an organic polymerization initiator are used together, the proportion of the organic polymerization initiator is preferably 70% by weight or less, more preferably 50% by weight or less of the total polymerization initiator. If the proportion of the organic polymerization initiator exceeds 70% by weight, problems similar to those caused when the organic polymerization initiator is used alone are undesirable.
本発明における乳化重合に使用する乳化剤については特
に制限はなく、アニオン型、ノニオン型および両性型界
面活性剤のいずれも使用することがてきる。これらは単
独でも、あるいは２種以上を混合して使用することもで
きる。例えば、ラウリル硫酸ナトリウムなどの高級アル
コールの硫酸エステル塩、ドデシルベンゼンスルホン酸
ナトリウムなどのアルキルベンゼンスルホン酸塩、ジオ
クチルスルホコハク酸ナトリウムなどの脂肪族カルボン
酸エステルのスルホン酸塩などのアニオン型界面活性剤
、ポリエチレングリコールのアルキルエステル型、アル
キルフェニルエーテル型、アルキルエーテル型などのノ
ニオン型界面活性剤などを使用することかできる。また
、両性界面活性剤としては、アニオン部分としてカルボ
ン酸塩、硫酸エステル塩、スルホン酸塩、りん酸塩、り
ん酸エステル塩を、またカチオン部分としてアミン塩、
第４級アンモニウム塩をもつものを挙げることができる
。具体的には、アルキルベタインの塩としてラウリルベ
タイン、ステアリルベタイン、ココアミドプロピルベタ
イン、２−ウンデシルヒドロキシエチルイミダゾリウム
ベタインの塩が、またアミノ酸タイプのものとしてはラ
ウリル−β−アラニン、ステアリル−β−アラニン、ラ
ウリルジ（アミノエチル）グリシン、オクチルジ（アミ
ノエチル）グリシン、ジオクチルジ（アミノエチル）グ
リシンの塩を挙げることができる。The emulsifier used in the emulsion polymerization in the present invention is not particularly limited, and any of anionic, nonionic and amphoteric surfactants can be used. These can be used alone or in combination of two or more. For example, anionic surfactants such as sulfate ester salts of higher alcohols such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, sulfonates of aliphatic carboxylic acid esters such as sodium dioctyl sulfosuccinate, polyethylene Nonionic surfactants such as glycol alkyl ester type, alkylphenyl ether type, and alkyl ether type can be used. In addition, as amphoteric surfactants, carboxylates, sulfate ester salts, sulfonates, phosphates, phosphate ester salts are used as anionic moieties, and amine salts, phosphate ester salts are used as cationic moieties.
Examples include those having quaternary ammonium salts. Specifically, alkyl betaine salts include lauryl betaine, stearyl betaine, cocoamidopropyl betaine, and 2-undecylhydroxyethylimidazolium betaine salts, and amino acid types include lauryl-β-alanine and stearyl-β. - Mention may be made of the salts of alanine, lauryl di(aminoethyl)glycine, octyldi(aminoethyl)glycine, dioctyldi(aminoethyl)glycine.
これら乳化剤のうち、特にアルキルベンゼンスルホン酸
塩が好ましく使用される。さらに具体的には、ドデシル
ベンゼンスルホン酸ナトリウムなどが特に好ましく使用
される。このアルキルベンゼンスルホン酸塩は、他の界
面活性剤、例えば高級アルコールの硫酸エステル塩、脂
肪族カルボン酸エステルのスルホン酸塩などのアニオン
型界面活性剤あるいは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
エーテル型などのノニオン型界面活性剤などと併用して
もよい。Among these emulsifiers, alkylbenzene sulfonates are particularly preferably used. More specifically, sodium dodecylbenzenesulfonate and the like are particularly preferably used. This alkylbenzene sulfonate can be used with other surfactants, such as anionic surfactants such as higher alcohol sulfate ester salts, aliphatic carboxylic acid ester sulfonates, or polyethylene glycol alkyl ester, alkyl ether, and alkyl esters. It may be used in combination with a nonionic surfactant such as a phenyl ether type surfactant.
乳化剤の使用量は、全単量体１００重量部当り、通常０
．０５〜２重量部であり、好ましくは０，０５〜１重量
部である。乳化剤の使用量が２重量部を越えると、耐水
性が劣り、紙塗被組成物の泡立ちが著しくなって塗工時
に問題となる。なお、アルキルベンゼンスルホン酸塩を
他のアニオン型あるいはノニオン型界面活性剤と併用す
る場合、アルキルベンゼンスルホン酸塩の使用割合は全
乳化剤の５０重量％以上とするのが好ましい。The amount of emulsifier used is usually 0 per 100 parts by weight of total monomers.
．． 0.05 to 2 parts by weight, preferably 0.05 to 1 part by weight. If the amount of emulsifier used exceeds 2 parts by weight, the water resistance will be poor and the paper coating composition will foam significantly, causing problems during coating. In addition, when an alkylbenzene sulfonate is used in combination with another anionic or nonionic surfactant, the proportion of the alkylbenzene sulfonate used is preferably 50% by weight or more of the total emulsifier.
本発明における乳化重合に使用する重合連鎖移動剤とし
ては、例えば、オクチルメルカプタン、ｎ−ドデシルメ
ルカプタン、ｔ−ドデシルメルカプタン、ｎ−ヘキサデ
シルメルカプタン、ｎ−テトラデシルメルカプタン、ｔ
−テトラデシルメルカプタンなどのメルカプタン類；ジ
メチルキサントゲンジスルフィド、ジエチルキサントゲ
ンジスルフィド、ジイソプロピルキサントゲンジスルフ
ィドなどのキサントゲンジスルフィド類；テトラメチル
チウラムジスルフィド、テトラエチルチウラムジスルフ
ィド、テトラブチルチウラムジスルフィドなどのチウラ
ムジスルフィド類；四塩化炭素、臭化エチレンなどのハ
ロゲン化炭化水素類；ペンタフェニルエタンなどの炭化
水素類：およびアクロレイン、メタクロレイン、アリル
アルコール、２−エチルへキシルチオグリコレート、タ
ーピノーレン、α−テルピネン、γ−テルピネン、ジペ
ンテン、α−メチルスチレンダイマー（２−４−ジフェ
ニル−４−メチル−１−ペンテンか５０重量部以上のも
のか好ましい）、さらに９゜１０−ジヒドロアントラセ
ン、１，４−ジヒドロナフタレン、インデン、１．４−
シクロへキサジエン等の不飽和環状炭化水素化合物；キ
サンチン、２．５−ジヒドロフラン等の不飽和へテロ環
状化合物等が挙げられる。Examples of the polymerization chain transfer agent used in the emulsion polymerization in the present invention include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, and t-dodecyl mercaptan.
-Mercaptans such as tetradecyl mercaptan; halogenated hydrocarbons such as ethylene; hydrocarbons such as pentaphenylethane; and acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycolate, terpinolene, α-terpinene, γ-terpinene, dipentene, α - Methylstyrene dimer (preferably 50 parts by weight or more of 2-4-diphenyl-4-methyl-1-pentene), furthermore 9゜10-dihydroanthracene, 1,4-dihydronaphthalene, indene, 1.4-
Examples include unsaturated cyclic hydrocarbon compounds such as cyclohexadiene; unsaturated heterocyclic compounds such as xanthine and 2.5-dihydrofuran.
これらは単独でも、あるいは２種以上を組合わせても使
用することができる。These can be used alone or in combination of two or more.
これらのうち、メルカプタン類、キサントゲンジスルフ
ィド類、チウラムジスルフィド類、α−メチルスチレン
ダイマー類、不飽和環状炭化水素化合物類、不飽和へテ
ロ環状化合物類が好適に使用できる。Among these, mercaptans, xanthogen disulfides, thiuram disulfides, α-methylstyrene dimers, unsaturated cyclic hydrocarbon compounds, and unsaturated heterocyclic compounds can be preferably used.
本発明における重合連鎖移動剤の使用量は、全単量体１
００重量部当たり、０．１〜１０重量部、より好ましく
は０．２〜７重量部である。この重合連鎖移動剤の使用
量が０．１重量部未満ては、耐ブリスター性が劣り、一
方１０重量部を越えると乳化重合中に多量の凝固物が発
生し、共重合体ラテックスの製造が実質的に困難となる
。The amount of polymerization chain transfer agent used in the present invention is based on the total monomer 1
The amount is 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight per 00 parts by weight. If the amount of the polymerization chain transfer agent used is less than 0.1 parts by weight, the blister resistance will be poor, while if it exceeds 10 parts by weight, a large amount of coagulation will occur during emulsion polymerization, making it difficult to produce copolymer latex. It becomes practically difficult.
本発明における乳化重合方法およびその条件については
特に制限はなく、従来公知の方法および条件下において
実施することができる。There are no particular limitations on the emulsion polymerization method and conditions in the present invention, and the emulsion polymerization can be carried out under conventionally known methods and conditions.
例えば、重合連鎖移動剤の添加方法については、−括添
加方式、分割添加方式、連続添加方式あるいはこれらの
組合わせのいずれでもよい。For example, the method of adding the polymer chain transfer agent may be a batch addition method, a divided addition method, a continuous addition method, or a combination thereof.
また、単量体の添加方法については、−括添加方式、分
割添加方式、連続添加方式あるいはこれらの組合せのい
ずれでもよい。これらの方式のうち、凝固物の生成の減
少、反応熱の除去などの点からは、分割添加方式または
連続添加方式が好ましい。さらに、エチレン系不飽和カ
ルボン酸単量体の全量または一部を含む単量体の１０〜
５０重量部を１段目で重合し、２段目では残りの単量体
５０〜９０重量部を連続的に添加して乳化重合する２段
重合方法によれば、重合工程における凝固物の生成がよ
り一層減少でき、本発明が目的とする紙塗被組成物が効
果的に得られることから、この２段重合方法によって本
発明の乳化重合を実施するのが好ましい。The monomer addition method may be a batch addition method, a divided addition method, a continuous addition method, or a combination thereof. Among these methods, the divided addition method or the continuous addition method is preferable from the viewpoint of reducing the formation of coagulum and removing the heat of reaction. Furthermore, 10 to 100% of the monomer containing the whole or a part of the ethylenically unsaturated carboxylic acid monomer
According to a two-stage polymerization method in which 50 parts by weight of the monomer is polymerized in the first stage, and the remaining 50 to 90 parts by weight of the monomer is continuously added in the second stage for emulsion polymerization, the formation of a coagulated product in the polymerization process is It is preferable to carry out the emulsion polymerization of the present invention by this two-stage polymerization method, since this can further reduce the amount of paper coating composition intended by the present invention.
なお、本発明の製造方法において２段重合方法を採用す
る場合には、有機溶剤は１段目および２段目のいずれか
一方の段階で添加してもよく、あるいは両方の段階で添
加してもよい。In addition, when adopting a two-stage polymerization method in the production method of the present invention, the organic solvent may be added at either the first stage or the second stage, or it may be added at both stages. Good too.
また、シードラテックスおよび本発明の有機溶剤の存在
下において前述した単量体を重合する、いわゆるシード
重合方法を採用してもよい。上記のシードラテックスの
単量体組成としては、好ましくは、エチレン系不飽和カ
ルボン酸単量体０１〜１０重量％、前記単量体成分（ａ
）および／または（ｂ）５０〜９９．９重量％、エチレ
ン系不飽和架橋性単量体０〜４０重量％、好ましくは０
．１〜４０重量％である。シードラテックスの使用量は
、該シードラテックスの存在下で重合する全単量体１０
０重量部に対して、好ましくは０．０５〜２０重量部（
固形分）である。Alternatively, a so-called seed polymerization method may be employed in which the monomers described above are polymerized in the presence of seed latex and the organic solvent of the present invention. The monomer composition of the seed latex preferably includes 01 to 10% by weight of ethylenically unsaturated carboxylic acid monomer, and the monomer component (a
) and/or (b) 50 to 99.9% by weight, 0 to 40% by weight of ethylenically unsaturated crosslinkable monomer, preferably 0
．． It is 1 to 40% by weight. The amount of seed latex used is 10% of the total monomers polymerized in the presence of the seed latex.
0 parts by weight, preferably 0.05 to 20 parts by weight (
solid content).
前記エチレン系不飽和架橋性単量体としては、好ましく
はジビニルベンゼン、エチレングリコールジメタクリレ
ートおよびトリメチロールプロパントリメタクリレート
、さらに好ましくはジビニルベンゼンである。The ethylenically unsaturated crosslinkable monomer is preferably divinylbenzene, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate, more preferably divinylbenzene.
本発明において、重合段階で使用された有機溶剤は、重
合終了後、スチームストリッピング、減圧蒸溜等の方法
により除去されることが好ましい。In the present invention, the organic solvent used in the polymerization step is preferably removed by steam stripping, vacuum distillation, or the like after the polymerization is completed.
このとき、有機溶剤の残留量は、得られる共重合体１０
０重量部に対して、好ましくは１重量部未満、さらに好
ましくは０．５重量部未満、特に好ましくは０．２重量
部未満とする。At this time, the amount of residual organic solvent is 10
The amount is preferably less than 1 part by weight, more preferably less than 0.5 part by weight, particularly preferably less than 0.2 part by weight.
［実施例］ 以下、実施例を挙げて本発明を更に具体的に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
なお、実施例中の「％」および「部」は重量基準である
。Note that "%" and "part" in the examples are based on weight.
〈実施例１〜７．比較例１〜４〉
（共重合体ラテックスＡ−Ｇ、ａ−ｄの製造）１００！
の耐圧反応器に水１５０部を仕込み、さらに表１に示す
１段目成分（単量体１重合連鎖移動剤１重合開始剤、乳
化剤、有機溶剤）を仕込んだ後、窒素雰囲気中で温度７
０℃で２時間重合した。<Examples 1 to 7. Comparative Examples 1 to 4> (Production of copolymer latex A-G, ad) 100!
After charging 150 parts of water into a pressure-resistant reactor, and further charging the first stage components shown in Table 1 (monomer 1 polymerization chain transfer agent 1 polymerization initiator, emulsifier, organic solvent), the reactor was heated at a temperature of 7 in a nitrogen atmosphere.
Polymerization was carried out at 0°C for 2 hours.
次に、２段目成分の単量体および重合連鎖移動剤を８時
間かけて連続的に添加して重合を行った。Next, the second-stage component monomer and polymerization chain transfer agent were continuously added over 8 hours to perform polymerization.
なお、添加開始後５時間口に２段目成分の乳化剤を一括
添加した。その後、重合を完結させるため、さらに３時
間反応を継続し、重合転化率９８％で重合を終了した。Incidentally, the emulsifier as the second stage component was added at once to the mouth 5 hours after the start of addition. Thereafter, in order to complete the polymerization, the reaction was continued for an additional 3 hours, and the polymerization was completed at a polymerization conversion rate of 98%.
得られた共重合体ラテックスを水酸化ナトリウムを用い
てｐｎ ７．５に調整した後、水蒸気を吹き込んで未反
応単量体および有機溶剤を除去し、さらに加熱減圧蒸溜
によって固形分濃度５０％に調製し、本発明の実施例に
かかる７種の共重合体ラテックスＡ−Ｇおよび比較例に
かかる４種の共重合体ラテックスａ−ｄを得た。The obtained copolymer latex was adjusted to pn 7.5 using sodium hydroxide, then steam was blown in to remove unreacted monomers and organic solvents, and the solid content concentration was reduced to 50% by heating and vacuum distillation. Seven types of copolymer latexes A to G according to examples of the present invention and four types of copolymer latexes ad according to comparative examples were obtained.
得られた各共重合体ラテックスについて、下記の方法に
よりそのゲル含量、有機溶剤残留量および臭気の発生状
態を調べ、その結果を表２に示した。なお、比較例４て
有機溶剤として用いられるエチレングリコールの沸点は
１９７℃、溶解パラメーターは１４．７である。Each of the obtained copolymer latexes was examined for gel content, residual amount of organic solvent, and odor generation by the following methods, and the results are shown in Table 2. In addition, the boiling point of ethylene glycol used as the organic solvent in Comparative Example 4 is 197° C., and the solubility parameter is 14.7.
ゲル含量
共重合体ラテックスをｐｔ＋ ｇ、ｏに調整した後、イ
ソプロパツールで凝固し、洗浄した後、乾燥した。After adjusting the gel content of the copolymer latex to pt+g,o, it was coagulated with isopropanol, washed, and dried.
次に、約０．３ｇの試料を採取し、１００ ｍｌのトル
エンに２０時間浸漬した後、トルエン不溶分を測定し、
試料に対する割合（％）を求めてゲル含量とした。Next, about 0.3 g of sample was taken and immersed in 100 ml of toluene for 20 hours, and the toluene insoluble content was measured.
The gel content was determined by calculating the ratio (%) to the sample.
有機溶剤残留量
ガスクロマド法により共重合体ラテックスにおける有機
溶剤量（％）を測定した。Amount of residual organic solvent The amount (%) of organic solvent in the copolymer latex was measured by gas chromatography.
臭 気
共重合体ラテックスを、コーティングロッドを用いてポ
リエステルフィルム上に塗被量１０ｇ／ゴでクリアコー
ティングし、１２０℃で３０秒間乾燥したときの臭気を
臭覚により判定し、下記の３段階で評価した。Odor The odor copolymer latex was clear-coated on a polyester film at a coating weight of 10 g/g using a coating rod and dried at 120°C for 30 seconds.The odor was judged by the sense of smell and evaluated on the following 3 scales. did.
Ｏ：はとんど臭気を感じない
△：やや臭気を感しる
×：強い臭気を感しる
（紙塗被組成物の調整）
上記共重合体ラテックスＡ−Ｈ，ａ−ｄを用いて下記の
処方により紙塗被組成物（塗料）を調製した。O: Almost no odor △: Slight odor x: Strong odor (adjustment of paper coating composition) Using the above copolymer latex A-H, a-d A paper coating composition (paint) was prepared according to the following formulation.
配合処方
クレー ８０部
炭酸カルシウム ２０部
共重合体ラテックス １０部
酸化デンプン ５部
ビロリン酸ナトリウム ０．５部水
全固形分が６０％になる量
得られた塗料は、下記試験方法で評価した。その結果を
表２に示した。なお、試験に使用したコート紙は、塗料
を坪量６４ ｇ＃＋ｆの原紙にコーティングブレードを
用いて塗被量２０ｇ／ｒｒｒで塗工して得た。Mixed recipe Clay 80 parts Calcium carbonate 20 parts Copolymer latex 10 parts Oxidized starch 5 parts Sodium birophosphate 0.5 parts Water
The paint obtained in an amount with a total solids content of 60% was evaluated by the following test method. The results are shown in Table 2. The coated paper used in the test was obtained by applying the paint to a base paper with a basis weight of 64 g#+f using a coating blade at a coating amount of 20 g/rrr.
■ ドライビック（接着強度の指標）
Ｒ１印刷機で印刷したときのピッキングの程度を肉眼で
判定し、５段階法で評価した。点数の高いものほど良好
である。点数は測定回数６回の平均値で示した。■Dry Vic (adhesive strength index) The degree of picking when printed with the R1 printing machine was visually judged and evaluated using a 5-step method. The higher the score, the better. The score was expressed as the average value of 6 measurements.
■ ＲＩウェットビック（耐水性の指標）ＲＩ印刷機で
モルトンロールを用い湿し水を与えて印刷したときのピ
ッキングの程度を肉眼で判定し、５段階法で評価した。(2) RI Wet Vic (indicator of water resistance) The degree of picking when printed using a Morton roll with an RI printing machine and applying dampening water was visually judged and evaluated using a five-point scale.
点数の高いものほど良好である。点数は測定回数６回の
平均値で示した。The higher the score, the better. The score was expressed as the average value of 6 measurements.
■ 耐ブリスター性
両面印刷塗工紙を調／ｆｊ（約６％）した後、加熱オイ
ルバスに投げ込み、ブリスターが発生するときの最低温
度を示した。■ Blister resistance After double-sided printing coated paper was adjusted to fj (approximately 6%), it was thrown into a heated oil bath, and the lowest temperature at which blistering occurred was determined.
実施例１〜７は本発明の範囲内の有機溶剤を使用して製
造した共重合体ラテックスを使用した例であり、比較例
１〜３は有機溶剤を使用せずに製造した共重合体ラテッ
クスを使用した例であり、比較例４は本発明の範囲外の
有機溶剤を使用して製造した共重合体ラテックスを使用
した例である。Examples 1 to 7 are examples using copolymer latexes produced using organic solvents within the scope of the present invention, and Comparative Examples 1 to 3 are copolymer latexes produced without using organic solvents. Comparative Example 4 is an example in which a copolymer latex produced using an organic solvent outside the scope of the present invention was used.
なお、比較例１，２は、実施例１，２とそれぞれ単量体
組成および重合連鎖移動剤の種類の点で対応している。Note that Comparative Examples 1 and 2 correspond to Examples 1 and 2 in terms of monomer composition and type of polymerization chain transfer agent, respectively.
実施例１〜７は、比較例１〜４に比べ、同一あるいは近
似の単量体組成において重合連鎖移動剤の使用量が少な
いかあるいは同じにもかかわらず、ゲル含量が低くなっ
ており、重合連鎖移動剤の効率が高まっていることがわ
かる。Compared to Comparative Examples 1 to 4, Examples 1 to 7 have the same or similar monomer composition and the amount of polymerization chain transfer agent used is smaller or the same, but the gel content is lower, and the polymerization It can be seen that the efficiency of the chain transfer agent has increased.
また、得られた共重合体ラテックスの塗膜乾燥時の臭気
については、実施例においては重合連鎖移動剤の使用量
が比較例に比べて相対的に減るため、かなり改善されて
いる。Furthermore, the odor during drying of the coating film of the obtained copolymer latex was considerably improved in the examples because the amount of polymer chain transfer agent used was relatively reduced compared to the comparative examples.
さらに、コート紙の物性においても、接着強度、耐水性
、耐ブリスター性の点て、実施例は比較例より全般的に
優れていることがわかる。Furthermore, regarding the physical properties of the coated paper, it can be seen that the Examples are generally superior to the Comparative Examples in terms of adhesive strength, water resistance, and blister resistance.
［発明の効果］
本発明によれば、重合時に特定の有機溶剤を用いること
により、重合連鎖移動剤の使用量を相対的に低減するこ
とが可能となる。その結果、重合連鎖移動剤に起因する
問題点を改良することができ、例えば、得られた共重合
体ラテックスの臭気が低減でき、さらに接着強度、耐水
性および耐ブリスター性等の塗膜物性の改善を図ること
ができ、各種の接着剤として有用である。[Effects of the Invention] According to the present invention, by using a specific organic solvent during polymerization, it is possible to relatively reduce the amount of the polymerization chain transfer agent used. As a result, problems caused by polymer chain transfer agents can be improved, for example, the odor of the obtained copolymer latex can be reduced, and physical properties of the coating film such as adhesive strength, water resistance, and blister resistance can be improved. It is useful as various adhesives.
本発明によって得れる共重合体ラテックスは、特に、コ
ート紙、コート板紙の紙塗被組成物のバインダーとして
好適に使用することができ、さらにカーペットバッキン
グ剤、塗料、工業用および家庭用接着剤等の各種接着剤
用途に使用できる。The copolymer latex obtained by the present invention can be particularly suitably used as a binder for paper coating compositions for coated paper and coated paperboard, as well as carpet backing agents, paints, industrial and household adhesives, etc. Can be used for various adhesive applications.
Claims (1)
．５〜２０重量部と、 の存在下で乳化重合することを特徴とする共重合体ラテ
ックスの製造方法。(1) When emulsion polymerizing 100 parts by weight of monomers containing (a) 10 to 80 parts by weight of a conjugated diene monomer (b) 20 to 90 parts by weight of an ethylenically unsaturated monomer, a polymerization chain transfer agent is used. 0.1 to 10 parts by weight and 0 water-soluble ethers and/or monoalcohols
．． A method for producing a copolymer latex, comprising emulsion polymerization in the presence of 5 to 20 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28941990A JP2926963B2 (en) | 1990-10-26 | 1990-10-26 | Method for producing copolymer latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28941990A JP2926963B2 (en) | 1990-10-26 | 1990-10-26 | Method for producing copolymer latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04161403A true JPH04161403A (en) | 1992-06-04 |
| JP2926963B2 JP2926963B2 (en) | 1999-07-28 |
Family
ID=17743001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28941990A Expired - Lifetime JP2926963B2 (en) | 1990-10-26 | 1990-10-26 | Method for producing copolymer latex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2926963B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06220112A (en) * | 1993-01-26 | 1994-08-09 | Nippon Zeon Co Ltd | Production of copolymer latex |
| US5521268A (en) * | 1995-03-29 | 1996-05-28 | Eastman Kodak Company | Odor reduction in toner polymers |
| JPH11162794A (en) * | 1997-12-01 | 1999-06-18 | Jsr Corp | Binder for electric double layer capacitor electrode |
-
1990
- 1990-10-26 JP JP28941990A patent/JP2926963B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06220112A (en) * | 1993-01-26 | 1994-08-09 | Nippon Zeon Co Ltd | Production of copolymer latex |
| US5521268A (en) * | 1995-03-29 | 1996-05-28 | Eastman Kodak Company | Odor reduction in toner polymers |
| JPH11162794A (en) * | 1997-12-01 | 1999-06-18 | Jsr Corp | Binder for electric double layer capacitor electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2926963B2 (en) | 1999-07-28 |
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