JPH0441512A - Production of diene copolymer latex - Google Patents
Production of diene copolymer latexInfo
- Publication number
- JPH0441512A JPH0441512A JP14860490A JP14860490A JPH0441512A JP H0441512 A JPH0441512 A JP H0441512A JP 14860490 A JP14860490 A JP 14860490A JP 14860490 A JP14860490 A JP 14860490A JP H0441512 A JPH0441512 A JP H0441512A
- Authority
- JP
- Japan
- Prior art keywords
- component
- chain transfer
- copolymer latex
- transfer agent
- mixture
- 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 39
- 229920000126 latex Polymers 0.000 title claims abstract description 39
- 229920001577 copolymer Polymers 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- -1 diene compound Chemical class 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 150000001356 alkyl thiols Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003505 polymerization initiator Substances 0.000 abstract description 3
- 125000004414 alkyl thio group Chemical group 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000007639 printing Methods 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-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
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 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
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical class CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、共重合体ラテックスの製造法の改良に関する
ものである。さらに詳しくいえは、本発明は、紙塗工用
、カーペットバックサイジング用、繊維結合用などのバ
インダーとして好適な高性能の共重合体ラテックスを効
率よく製造する方法に関するものでおる。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for producing copolymer latex. More specifically, the present invention relates to a method for efficiently producing a high-performance copolymer latex suitable as a binder for paper coating, carpet back sizing, fiber binding, etc.
従来の技術
従来、合成共重合体ラテックスは、例えは紙塗工用バイ
ンダー、カーペンドパ・り→ノイジング用バインター、
不織布や人工皮革なとの繊維結合用バインター、あるい
は各種材料の粘接着剤なととして広く用いられている。Conventional technology Conventionally, synthetic copolymer latex has been used, for example, as a binder for paper coating, as a binder for carpendopa resin, and as a binder for noising.
It is widely used as a binder for binding fibers such as non-woven fabrics and artificial leather, and as an adhesive for various materials.
そして、共重合体ラテックスがこのような用途lこ用い
られる場合、該共重合体ラテックスは、接着強度か高イ
、かつ耐水性、乾燥加熱による耐ブリスター性なとに優
れていることが要求される。When copolymer latex is used for such purposes, it is required that the copolymer latex has high adhesive strength and excellent water resistance and blister resistance due to dry heating. Ru.
例えば、塗工紙は、紙の印刷適性の向上及び光沢などの
光学的特性の向上を目的として、抄造された原紙表面に
、カオリンクレー、炭酸カル/ラム、サテンホワイト、
タルク、酸化チタンなどの顔料、それらのバインダーと
しての共重合体ラテックス及び保水剤あるいは補助バイ
ンダーとしてのスターチ、カゼイン、ポリビニルアルコ
ール、カルポキシメチルセルロースなどの水溶性高分子
を主構成成分とする塗料が塗工されたものであって、該
共重合体ラテックスとして従来からスチレンとブタジェ
ンを主要単量体成分とし、これらを乳化重合して得られ
たスチレン−ブタジェン系共重合体ラテックス、いわゆ
るSB系ラテックスが汎用的に用いられている。For example, coated paper uses kaolin clay, cal/rum carbonate, satin white,
Paints whose main components are pigments such as talc and titanium oxide, their copolymer latex as a binder, starch as a water-retaining agent or auxiliary binder, and water-soluble polymers such as casein, polyvinyl alcohol, and carboxymethylcellulose are coated. Conventionally, styrene-butadiene copolymer latex, so-called SB latex, is produced by emulsion polymerization of styrene and butadiene as main monomer components. Used for general purposes.
ところで、近年、カラー印刷された雑誌類やパンフレッ
ト、広告類の需要の拡大に伴って塗工紙の生産が著しく
増大している。特に、オフセット印刷での高速印刷化傾
向に伴い、塗工紙及び顔料バインダーの品質に対する要
求水準もますます高度化しており、そのため、塗工紙の
品質の中でも特にインクピック抵抗性、いわゆるピック
強度の向上が強く求められている。しかも、このピック
強度性能は他の印刷物性、すなわち湿潤ピック強度、耐
ブリスター性、網点再現性などとは負の相関関係にある
ため、これらの諸物性を高水準にバランス化させる改良
が一段と要求されている。Incidentally, in recent years, the production of coated paper has increased significantly as demand for color-printed magazines, pamphlets, and advertisements has increased. In particular, with the trend toward higher speed printing in offset printing, the quality requirements for coated paper and pigment binders are becoming increasingly sophisticated. There is a strong need for improvement. Moreover, this pick strength performance has a negative correlation with other print properties, such as wet pick strength, blister resistance, halftone dot reproducibility, etc., so improvements that balance these physical properties to a high level are required. requested.
塗工紙のこれらの性質は、顔料バインダーとして用いら
れるSB系ラテックスの性能に特に強く依存することか
ら、これまで該SB系ラテックスの性能について種々の
検討がなされてきた。Since these properties of coated paper are particularly strongly dependent on the performance of the SB latex used as a pigment binder, various studies have been made on the performance of the SB latex.
例えば、共重合体ラテックスの皮膜のベンゼン、トルエ
ン、テトラヒドロフランなどの溶剤に対する不溶解部分
の割合がピック強度と耐ブリスター性の支配因子である
ことが確認されていることから、この面より種々の検討
がなされており、具体的にはラテックス中の共重合体の
組成及びゲル分率を特定の範囲に調整することにより、
優れた性能を発揮させることが提案されている(特公昭
59−3598号公報、特公昭60−17879号公報
、特開昭58−4894号公報)。このラテックスのゲ
ル分率は単量体組成、重合温度をはじめとした様々な重
合因子によって変化するが、これを所望の水準に調整す
る方法は連鎖移動剤の添加が一般的かつ簡便である。For example, it has been confirmed that the proportion of the insoluble portion of the copolymer latex film in solvents such as benzene, toluene, and tetrahydrofuran is the controlling factor for pick strength and blister resistance, and various studies have been conducted from this point of view. Specifically, by adjusting the composition and gel fraction of the copolymer in the latex to a specific range,
It has been proposed to exhibit excellent performance (Japanese Patent Publication No. 59-3598, Japanese Patent Publication No. 60-17879, Japanese Patent Application Laid-open No. 58-4894). The gel fraction of this latex varies depending on various polymerization factors such as monomer composition and polymerization temperature, but a common and simple method for adjusting it to a desired level is to add a chain transfer agent.
しかしながら、連鎖移動剤の量により該ゲル分率を調整
した場合、−船釣には塗工紙のピンク強度は、SBラテ
ックスにおいてそのゲル分率が75〜95重量%の範囲
で最も高くなるのに対して、耐ブリスター性はゲル分率
の低いものほど良好となることが認められており、ピッ
ク強度と耐ブリスター性の両方を同時に高い水準にまで
向上させるには、前記技術は、いずれも十分に満足しう
るものではない。However, when the gel fraction is adjusted by the amount of chain transfer agent, the pink strength of coated paper for boat fishing is highest when the gel fraction is in the range of 75 to 95% by weight in SB latex. On the other hand, it is recognized that the lower the gel fraction, the better the blister resistance is.In order to simultaneously improve both pick strength and blister resistance to a high level, none of the above technologies can be used. It's not completely satisfying.
他方、カーペットバックサイジング用接着剤は、一般に
共重合体ラテックスに炭酸カルシウム又は水酸化アルミ
ニウムなどの充てん剤及び増粘剤なとの他の添加剤を配
合した組成物であって、タフテッドカーペット、ニード
ルパンチカーペットなどの製造において、主にパイル(
ふさ糸)の脱落防止並びにジュートなどの二次基布との
接着のために用いられる。したがって、この場合カーペ
ットの最重要物性である接着強度の向上が当業界での最
大の技術課題の1つであり、そのため、共重合体ラテッ
クス及び組成物の配合面からの改良検討がなされている
が、これまで満足できる水準のものが得られていないの
が実状である。On the other hand, carpet back sizing adhesives are generally compositions of copolymer latex with other additives such as fillers such as calcium carbonate or aluminum hydroxide and thickeners, and are suitable for use in tufted carpets, In the production of needle punch carpets, etc., pile (
It is used to prevent tassels from falling off and to adhere to secondary base fabrics such as jute. Therefore, in this case, improving adhesive strength, which is the most important physical property of carpet, is one of the biggest technical challenges in this industry, and therefore, improvements are being considered from the aspect of blending copolymer latex and compositions. However, the reality is that a satisfactory level has not been obtained so far.
このように、従来技術では塗工紙の印刷のより一層の高
速化に対応することかできず、高品質の塗工紙の製造を
可能にするバインダーとしての共重合体ラテックスの出
現が強く求められており、また、カーペット並びに粘接
着剤においても同様に高接着力を有する共重合体ラテン
クスの出現が望まれている。As described above, conventional technologies cannot cope with the ever-increasing printing speed of coated paper, and there is a strong need for the emergence of copolymer latex as a binder that enables the production of high-quality coated paper. Furthermore, it is desired that copolymer Latinx having high adhesive strength be developed for carpets and adhesives as well.
発明が解決しようとする課題
本発明はこのような事情のもとで、印刷用塗工紙におけ
るピンク強度と他の性能とのバランスや、カーペットバ
ックサイジング及び粘接着剤における接着力をより向上
させるための高性能の共重合体ラテックス全提供するこ
とを目的としてなされたものである。Problems to be Solved by the Invention Under these circumstances, the present invention aims to further improve the balance between pink strength and other properties in coated printing paper, and the adhesive strength in carpet back sizing and adhesives. The purpose of this work is to provide a high-performance copolymer latex for all applications.
課題を解決するための手段
本発明者らは、前記の好ましい性質を有する共重合体ラ
テックスを開発すべく鋭意研究を重ねた結果、乳化重合
によりジエン系共重合体ラテックスを製造するに際し、
特定の2種類の連鎖移動剤を、順次重合系内に添加する
ことにより、その目的を達成しうろことを見い出し、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 Problems As a result of intensive research to develop a copolymer latex having the above-mentioned preferred properties, the present inventors found that when producing a diene copolymer latex by emulsion polymerization,
It was discovered that the objective could be achieved by sequentially adding two specific types of chain transfer agents into the polymerization system, and based on this knowledge, the present invention was completed.
すなわち、本発明は、水性媒体中において、共役ジエン
化合物、エチレン性不飽和カルボン酸及び他の共重合可
能な単量体を乳化重合させてジエン系共重合体ラテック
スを製造するに当り、(a)第1段階として追加添加す
る全単量体混合物の50〜80重量%とアルキルチオー
ル系連鎖移動剤との混合物を添加し、次いで(b)第2
段階として追加添加する単量体混合物の残部とアルキル
チオール系以外の連鎖移動剤との混合物を添加すること
を特徴とするジエン系共重合体ラテックスの製造法を提
供するものである。That is, the present invention provides a method for producing a diene copolymer latex by emulsion polymerizing a conjugated diene compound, an ethylenically unsaturated carboxylic acid, and other copolymerizable monomers in an aqueous medium. ) A mixture of 50 to 80% by weight of the total monomer mixture to be additionally added and an alkylthiol chain transfer agent is added as a first step, and then (b) a second step is performed.
The present invention provides a method for producing a diene-based copolymer latex, which is characterized in that a mixture of the remainder of the monomer mixture and a chain transfer agent other than an alkylthiol-based chain transfer agent is added as a step.
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アルキルチオール系連鎖移動
剤としては、例えば[−ドデシルメルカプタン、n−ド
デシルメルカプタン、メルカプトエタノールなどのアル
キルメルカプタン、テトラチオグリコール酸ペンタエリ
トリトールなどのチオグリコール酸エステルなどを挙げ
ることができる。Examples of the alkylthiol chain transfer agent used in the present invention include alkyl mercaptans such as [-dodecylmercaptan, n-dodecylmercaptan, and mercaptoethanol, and thioglycolic acid esters such as pentaerythritol tetrathioglycolate. can.
また、本発明において使用される前記アルキルチオール
系以外の連鎖移動剤としては、例えば四塩化炭素などの
ハロゲン化合物、2.4−ジフェニル4−メチル−1−
ペンテンなとの核置換α−メチルスチレンダイマー、エ
チルベンゼンなどの芳香族化合物、ナフトール及びその
核置換誘導体などを挙げることができる。Chain transfer agents other than the alkylthiol type used in the present invention include, for example, halogen compounds such as carbon tetrachloride, 2,4-diphenyl4-methyl-1-
Examples include nuclear-substituted α-methylstyrene dimer with pentene, aromatic compounds such as ethylbenzene, naphthol and its nuclear-substituted derivatives, and the like.
前記アルキルチオール系連鎖移動剤は1種用いてもよい
し、2種以上を組み合わせて用いてもよく、またその使
用量は、通常単量体合計量10011F量部当り、0.
1〜0.2重量部、好ましくは0.1〜1.0重量部の
範囲で選ばれる。一方、前記アルキルチオール系以外の
連鎖移動剤は1種用いてもよいし、2種以上を組み合わ
せて用いてもよく、またその使用量は、通常0.2〜l
O重量部、好ましくは0.2〜5重量部の範囲で選ばれ
る。The alkylthiol-based chain transfer agent may be used alone or in combination of two or more, and the amount used is usually 0.1 parts per 10011 F parts of the total amount of monomers.
The amount is selected in the range of 1 to 0.2 parts by weight, preferably 0.1 to 1.0 parts by weight. On the other hand, one type of chain transfer agent other than the alkylthiol type may be used, or two or more types may be used in combination, and the amount used is usually 0.2 to 1
0 parts by weight, preferably in the range of 0.2 to 5 parts by weight.
本発明においては、まず(a)第1段階として追加添加
する全単量体混合物の50〜80重量%と前記アルキル
チオール系連鎖移動剤との混合物を添加し、次いで、(
b)第2段階として、追加添加する連鎖移動剤の残部と
前記のアルキルチオール系以外の連鎖移動剤との混合物
を添加することが必要である。このように、2種類の連
鎖移動剤を順次重合系に添加することによって、本発明
の目的が達せられる。In the present invention, first, (a) a mixture of 50 to 80% by weight of the total monomer mixture to be additionally added and the alkylthiol chain transfer agent is added as the first step, and then (
b) As a second step, it is necessary to add a mixture of the remainder of the additional chain transfer agent and the aforementioned chain transfer agent other than the alkylthiol type. Thus, the objects of the present invention can be achieved by sequentially adding two types of chain transfer agents to the polymerization system.
本発明において用いられる共役ジエン化合物としては、
例えばブタジェン、イソプレン、2−クロロ−1,3−
ブタジェンなどが挙げられる。これらの共役ジエン化合
物は、1種用いてもよいし、2種以上を組み合わせても
よく、また、その使用量は全単量体の重量に基づき5〜
90重量%の範囲にあることが望ましい。さらに塗工紙
用共重合体ラテックスの場合、この共役ジエン化合物の
より好ましい使用量は20〜70重量%の範囲で選ばれ
る。The conjugated diene compounds used in the present invention include:
For example, butadiene, isoprene, 2-chloro-1,3-
Examples include butadiene. These conjugated diene compounds may be used alone or in combination of two or more, and the amount used is 5 to 50% based on the weight of all monomers.
It is desirable that the content be in the range of 90% by weight. Furthermore, in the case of a copolymer latex for coated paper, a more preferable amount of the conjugated diene compound to be used is selected within the range of 20 to 70% by weight.
本発明において用いられるエチレン性不飽和カルボン酸
としては、例えばアクリル酸、メタクリル酸、イタコン
酸、クロトン酸なとの一塩基性カルボン酸、マレイン際
、フマル酸なとの二塩基性カルボン酸及びそのモノエス
テルなどを挙げることができる。これらのエチレン性不
飽和カルボン酸は1種用いてもよいし、2種以上を組み
合わせて用いてもよく、またその使用量は、全中量体の
重量に基づき、通常0.2重量%以上、好ましくは0.
2〜15ffi量%の範囲で選はれる。Examples of the ethylenically unsaturated carboxylic acids used in the present invention include monobasic carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and crotonic acid; dibasic carboxylic acids such as maleic acid and fumaric acid; Examples include monoester. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more, and the amount used is usually 0.2% by weight or more based on the weight of the total intermediate. , preferably 0.
It is selected in the range of 2 to 15%ffi amount.
本発明におlJlて用いられる共重合可能な他の単量体
としては、芳香族モノヒニル化合物や・2゛ビニル化合
物、アクリル酸エステルやメタクリル酸エステル、/ア
ン化ビニル化合物類、エチレン性アミド類なとが挙げら
れる。Other copolymerizable monomers used in the present invention include aromatic monohinyl compounds, 2-vinyl compounds, acrylic acid esters, methacrylic acid esters, vinyl anhydride compounds, and ethylenic amides. Nato is mentioned.
該芳香族モノビニル化合物やジビニル化合物としては、
例えばスチレン、α−メヂルスチレン、クロロスチレン
、アルキルスチレン、ノビニルベンゼンなどが挙げられ
る。アクリル酸エステルやメタクリル酸エステルとして
は、例えはアクリル酸又はメタクリル酸のメチル、エチ
ル、プロピル、ブチル、2−エチルヘキ/ル、ヒドロキ
ノエチル、グリシジルエステノ呟 さらにはエチレング
リコルジアクリレート又ジメタクリレートなどが挙げら
れる。ノアン化ビニル化合物類としては、例えばアクリ
ロニトリルやメタグリコニトリルなどが、エチレン性ア
ミド類としては、例えばアクリルアミド、メタクリルア
ミド、N−メチロールアクリルアミド、N−メチロール
メタクリルアミドなどが挙げられる。As the aromatic monovinyl compound or divinyl compound,
Examples include styrene, α-methylstyrene, chlorostyrene, alkylstyrene, and novinylbenzene. Examples of acrylic esters and methacrylic esters include methyl, ethyl, propyl, butyl, 2-ethylhexyl, hydroquinoethyl, glycidyl ester, ethylene glycoldiacrylate, dimethacrylate, etc. of acrylic acid or methacrylic acid. can be mentioned. Examples of the noaninated vinyl compounds include acrylonitrile and metaglyconitrile, and examples of the ethylenic amides include acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide.
さらに、これらの単量体以外に、酢酸ビニルなどのビニ
ルエステル類、塩化ビニル、塩化ビニリデンなどのハロ
ゲン化ビニル類、アミノエチルアクリレート又はメタク
リレート、ジメチルアミノエチルアクリレート又はメタ
クリレート、ジエチルアミノエチルアクリレート又はメ
タクリレートなどのエチレン性アミン類、スチレンスル
ホン酸ナトリウムなども用いることができる。Furthermore, in addition to these monomers, vinyl esters such as vinyl acetate, vinyl chloride, vinyl halides such as vinylidene chloride, aminoethyl acrylate or methacrylate, dimethylaminoethyl acrylate or methacrylate, diethylaminoethyl acrylate or methacrylate, etc. Ethylenic amines, sodium styrene sulfonate, etc. can also be used.
これらの共重合可能な単量体は1種用いてもよいし、2
種以上を組み合わせて用いてもよい。One type of these copolymerizable monomers may be used, or two types of these copolymerizable monomers may be used.
You may use combinations of more than one species.
本発明においては、該共重合体ラテックスは、水性媒体
中において、前記共役ジエン化合物、エチレン性不飽和
カルボン酸及び共重合可能な他の単量体を乳化重合させ
ることにより得られる。この乳化重合については、連鎖
移動剤の添加が前記条件を満たしていればよく、特に制
限されず、従来公知の方法を用いることができる。In the present invention, the copolymer latex is obtained by emulsion polymerization of the conjugated diene compound, ethylenically unsaturated carboxylic acid, and other copolymerizable monomers in an aqueous medium. This emulsion polymerization is not particularly limited as long as the addition of the chain transfer agent satisfies the above conditions, and conventionally known methods can be used.
この共重合体ラテックス中の該共重合体の濃度は、通常
40〜60重量%の範囲で選ばれる。The concentration of the copolymer in the copolymer latex is usually selected in the range of 40 to 60% by weight.
本発明における共重合体ラテックスの平均粒子径は界面
活性剤やシードラテックスの使用割合などによって調整
することができ、一般にその使用割合を高くするほど生
成共重合体ラテックスの平均粒子径は小さくなる傾向が
ある。この平均粒子径は0.05〜1μm1好ましくは
0.07〜0−3μmの範囲にあるのが望ましい。The average particle diameter of the copolymer latex in the present invention can be adjusted by the proportion of surfactant and seed latex used, and generally, the higher the proportion used, the smaller the average particle diameter of the resulting copolymer latex tends to be. There is. The average particle size is desirably in the range of 0.05 to 1 μm, preferably 0.07 to 0-3 μm.
前記界面活性剤としては、例えば脂肪酸セッケン、ロジ
ン酸セッケン、アルキルスルホン酸塩、ジアルキルアリ
ールスルホン酸塩、アルキルスルホコハク酸塩、ポリオ
キシエチレンアルキル硫酸塩、ポリオキシエチレンアル
キルアリール硫酸塩などのアニオン性界面活性剤、ポリ
オキシエチレンアルキルエーテル、ポリオキシエチレン
アルキルアリールエーテル、ポリオキシエチレンソルビ
タン脂肪酸エステル、オキシエチレンオキシプロピレン
ブロックコボリマーなどのノニオン性界面活性剤が挙げ
られる。この界面活性剤は通常、アニオン性界面活性剤
単独又はアニオン性/ノニオン性の混合系で用いられ、
その使用量は全単量体の重量に基づき、通常0.05〜
2重量%の範囲で選ばれる。Examples of the surfactants include anionic surfactants such as fatty acid soaps, rosin acid soaps, alkyl sulfonates, dialkylaryl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkylaryl sulfates. Active agents, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, and oxyethylene oxypropylene block copolymer can be mentioned. This surfactant is usually used as an anionic surfactant alone or as an anionic/nonionic mixed system.
The amount used is based on the weight of all monomers, and is usually 0.05~
It is selected within the range of 2% by weight.
重合の開始に必要なラジカル重合開始剤は、熱又は還元
性物質によりラジカル分解して、単量体の付加重合を起
こさせる作用を有するものであり、このようなものとし
ては、例えば水溶性又は油溶性のベルオキソ二硫酸塩、
過酸化物、アゾビス化合物など、具体的にはベルオキソ
ニ硫酸カリウム、ベルオキソニ硫酸ナトリウム、ベルオ
キソニ硫酸アンモニウム、過酸化水素、第三ブチルヒド
ロベルオキンド、過酸化ベンゾイル、2.2−アゾビス
イソブチロニトリル、クメンヒドロペルオキシドなどが
挙げられるが、これらの中で特にベルオキソ二硫酸塩が
好適である。この重合開始剤の使用量は、全単量体の重
量に基づき通常0.2〜1.5重量%の範囲で選ばれる
。The radical polymerization initiator required to initiate polymerization is one that has the effect of causing addition polymerization of monomers by radical decomposition using heat or a reducing substance. Examples of such initiators include water-soluble or oil-soluble beroxodisulfate,
Peroxides, azobis compounds, etc., specifically potassium beroxonisulfate, sodium beloxonisulfate, ammonium beloxonisulfate, hydrogen peroxide, tertiary-butylhydroberoquinde, benzoyl peroxide, 2,2-azobisisobutyronitrile, Examples include cumene hydroperoxide, and among these, peroxodisulfate is particularly preferred. The amount of the polymerization initiator used is usually selected within the range of 0.2 to 1.5% by weight based on the weight of all monomers.
この乳化重合における重合温度は、通常60〜100°
Cの範囲で選ばれるが、重合速度の促進あるいはより低
温での重合を望む場合には、酸性亜硫酸ナトリウム、ア
スコルビン酸やその塩、エリソルビン酸やその塩、ロン
ガリノトなとの還元剤を重合開始剤に組み合わせて用い
る、いわゆるレドックス重合法を採用することができる
。The polymerization temperature in this emulsion polymerization is usually 60 to 100°
C. However, when accelerating the polymerization rate or polymerizing at a lower temperature, a reducing agent such as acidic sodium sulfite, ascorbic acid or its salts, erythorbic acid or its salts, or longarinoto can be used as a polymerization initiator. A so-called redox polymerization method, which is used in combination with
本発明においては、所望に応じ各種重合調整剤、例えば
水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウ
ム、炭酸ナトリウム、リン酸水素二ナトリウムなどのp
H調節剤やエチレンジアミン四酢酸ナトリウムなどの各
種キレート剤などを添加することができる。In the present invention, various polymerization regulators such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, disodium hydrogen phosphate, etc. can be used as desired.
Various chelating agents such as H regulators and sodium ethylenediaminetetraacetate can be added.
本発明により製造した共重合体ラテックスを紙塗工用塗
料のバインダーとして用いる場合には、通常行われてい
る方法、例えば分散剤を溶解させた水中に、無機顔料あ
るいは無機・有機顔料類、水溶性高分子化合物、各種添
加剤とともに該共重合体ラテックスを添加して混合し、
均質な分散液として用いる方法を採用することができる
。そして、この紙塗工用塗料は、各種プレードコータ−
ロールコータ−などを用いる通常の方法によって、原紙
に塗工することができる。When the copolymer latex produced according to the present invention is used as a binder for paper coating materials, it is possible to use a commonly used method, for example, adding an inorganic pigment or an inorganic/organic pigment to water in which a dispersant is dissolved. The copolymer latex is added and mixed together with a polymeric compound and various additives,
A method using a homogeneous dispersion can be adopted. This paper coating paint can be applied to various blade coaters.
The base paper can be coated by a conventional method using a roll coater or the like.
発明の効果
本発明によると、印刷用塗工紙におけるピック強度と他
の性能とのバランスや、カーペットIくツクサイジング
及び粘接着剤における接着力をより向上させうる高性能
の共重合体ラテックスを容易に得ることができる。Effects of the Invention According to the present invention, a high-performance copolymer latex that can further improve the balance between pick strength and other properties in coated printing paper, and the adhesive strength in carpet thickening and adhesives is provided. can be easily obtained.
実施例
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples.
なお、各特性は次のようにして求めた。In addition, each characteristic was calculated|required as follows.
紙塗工性能評価
(イ)耐ブリスター性
R[印刷試験機(明製作所製)を用いて塗工紙の両面を
印刷インク(大日本インキ社製Webb Zett黄)
0.3mQをべた刷りする。この印刷された塗工紙を適
当な大きさに裁断し、その試験片を所定の温度に調整し
たンリコンオイル恒温槽に浸してブリスターが発生する
か否かを観察する。恒温槽の温度を変化させてこの試験
を行い、ブリスターの発生温度を比較する。評価は10
点評価方法で行い、耐ブリスター性に優れるものほど高
得点とした。Paper coating performance evaluation (a) Blister resistance R [Printing ink (Webb Zett yellow, manufactured by Dainippon Ink Co., Ltd.) on both sides of coated paper using a printing tester (manufactured by Mei Seisakusho)
Print 0.3 mQ. This printed coated paper is cut to an appropriate size, and the test piece is immersed in a thermostatic oil bath adjusted to a predetermined temperature to observe whether or not blisters occur. This test is performed by changing the temperature of the constant temperature bath, and the temperature at which blisters occur is compared. Rating is 10
A point evaluation method was used, and the better the blister resistance, the higher the score.
(ロ) ドライピック強度
R1印刷試験機を用いて、印刷インク(集草色素社製S
Dスーパーデラックス50紅B;タック値18)0.4
mQを5回重ね刷りを行い、ゴムロールに現れたピッキ
ング状態を別の台紙に裏取りし、その状況を観察する。(b) Using a dry pick strength R1 printing tester, printing ink (S
D Super Deluxe 50 Beni B; Tack value 18) 0.4
MQ is overprinted 5 times, the picking state that appears on the rubber roll is reversed onto another mount, and the situation is observed.
評価はIO点評価法で行い、ピッキング現象の少ないも
のほど高得点とした。Evaluation was performed using the IO point evaluation method, and the fewer the picking phenomenon, the higher the score.
実施例、比較例1.2
直径0゜04μmのシード粒子の水性分散体(シード固
形分濃度25重量%)4重量部を、かくはん装置と温度
調節用ジャケットを取り付けた耐圧反応容器に入れ、さ
らに水70重量部、ラウリル硫酸ナトリウム0.2重量
部、フマル酸2.5重量部を仕込み、内温を80°Cに
昇温し、次いで第1表に示す単量体混合液(A)を2時
間で添加し、その後ひぎつづき単量体混合液(B)を2
時間で添加した。また別に、単量体混合液(A)の添加
開始と同時に、水15重量部、ベルオキソニ硫酸ナトリ
ウム1重量部、水酸化ナトリウム0.2重量部、ラウリ
ル硫酸ナトリウム0.1重量部から成る水溶液を5時間
で添加しt;。Examples, Comparative Example 1.2 4 parts by weight of an aqueous dispersion of seed particles having a diameter of 0°04 μm (seed solid content concentration 25% by weight) was placed in a pressure-resistant reaction vessel equipped with a stirring device and a temperature control jacket, and further Charge 70 parts by weight of water, 0.2 parts by weight of sodium lauryl sulfate, and 2.5 parts by weight of fumaric acid, raise the internal temperature to 80°C, and then add the monomer mixture (A) shown in Table 1. Add the monomer mixture (B) for 2 hours, and then add the monomer mixture (B) for 2 hours.
Added in time. Separately, at the same time as the addition of the monomer mixture (A) started, an aqueous solution consisting of 15 parts by weight of water, 1 part by weight of sodium beloxonisulfate, 0.2 parts by weight of sodium hydroxide, and 0.1 part by weight of sodium lauryl sulfate was added. Added after 5 hours.
そして重合開始から6時間経過した時点で冷却し、次い
で生成した共重合体ラテックスを水酸化ナトリウムでp
Hを調整し1:。After 6 hours from the start of polymerization, the copolymer latex was cooled, and the resulting copolymer latex was purified with sodium hydroxide.
Adjust H to 1:.
応用例
実施例及び比較例1.2で調製した共重合体ラテツクス
について、紙塗工用バインダーとしての性能評価を行っ
た。その結果を第4表に示す。Application Examples The copolymer latexes prepared in Examples and Comparative Examples 1.2 were evaluated for their performance as binders for paper coating. The results are shown in Table 4.
なお、塗工塗料は第2表に示す配合で、不揮発分濃度が
63重量%になる水量で高速かくはん機で調製した。塗
料のpHはアンモニウム水で9.0に調整しt;。この
塗料を用いての塗工紙の調製条件を第3表に示す。The coating material had the formulation shown in Table 2 and was prepared using a high-speed stirrer with an amount of water that gave a nonvolatile content concentration of 63% by weight. The pH of the paint was adjusted to 9.0 with ammonium water. Table 3 shows the conditions for preparing coated paper using this paint.
第4表から、本発明の共重合体ラテックスをバインダー
として用いた塗工紙はビック強度と他の物性が高度にバ
ランスされたものであることが理解される。From Table 4, it is understood that the coated paper using the copolymer latex of the present invention as a binder has a high balance of bulk strength and other physical properties.
第 2 表
注1)エンゲルハード社製「ウルトラホワイト90J2
)エンゲルハード社製「ウルトラコート」3)三基製粉
社製[ニスカロン# 1500J4)東亜合成化学社製
[アロンT −40J5)住友化学社製「スミレッツ6
36」6)日本食品加工社製r M S 4600J第
3 表
第
表Table 2 Note 1) “Ultra White 90J2” manufactured by Engelhard
) “Ultracoat” manufactured by Engelhard 3) “Niscallon #1500J4” manufactured by Sanki Seifun Co., Ltd. “Aron T-40J5” manufactured by Toagosei Kagaku Co., Ltd. “Sumilets 6” manufactured by Sumitomo Chemical Co., Ltd.
Table 3
Claims (1)
性不飽和カルボン酸及び他の共重合可能な単量体を乳化
重合させてジエン系共重合体ラテックスを製造するに当
り、(a)第1段階として追加添加する全単量体混合物
の50〜80重量%とアルキルチオール系連鎖移動剤と
の混合物を添加し、次いで(b)第2段階として追加添
加する単量体混合物の残部とアルキルチオール系以外の
連鎖移動剤との混合物を添加することを特徴とするジエ
ン系共重合体ラテックスの製造法。1. In producing a diene copolymer latex by emulsion polymerizing a conjugated diene compound, an ethylenically unsaturated carboxylic acid, and other copolymerizable monomers in an aqueous medium, (a) as the first step: A mixture of 50 to 80% by weight of the total monomer mixture to be additionally added and an alkylthiol-based chain transfer agent is then added, and then (b) the remainder of the monomer mixture to be additionally added and non-alkylthiol-based chain transfer agents are added as a second step. A method for producing a diene copolymer latex, which comprises adding a mixture of diene copolymer latex and a chain transfer agent.
Priority Applications (1)
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JP14860490A JP2933985B2 (en) | 1990-06-08 | 1990-06-08 | Method for producing diene copolymer latex |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14860490A JP2933985B2 (en) | 1990-06-08 | 1990-06-08 | Method for producing diene copolymer latex |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0441512A true JPH0441512A (en) | 1992-02-12 |
JP2933985B2 JP2933985B2 (en) | 1999-08-16 |
Family
ID=15456491
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JP14860490A Expired - Fee Related JP2933985B2 (en) | 1990-06-08 | 1990-06-08 | Method for producing diene copolymer latex |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996006868A1 (en) * | 1994-08-29 | 1996-03-07 | Nippon Zeon Co., Ltd. | Unsaturated nitrile-conjugated diene copolymer, process for producing the same, and vulcanizable rubber composition |
US5739232A (en) * | 1994-03-04 | 1998-04-14 | Sartomer Company | Water based compositions with improved substrate adhesion |
JP2012007172A (en) * | 2011-08-15 | 2012-01-12 | Asahi Kasei Chemicals Corp | Copolymer latex and composition for paper coating |
-
1990
- 1990-06-08 JP JP14860490A patent/JP2933985B2/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5739232A (en) * | 1994-03-04 | 1998-04-14 | Sartomer Company | Water based compositions with improved substrate adhesion |
WO1996006868A1 (en) * | 1994-08-29 | 1996-03-07 | Nippon Zeon Co., Ltd. | Unsaturated nitrile-conjugated diene copolymer, process for producing the same, and vulcanizable rubber composition |
WO1996006869A1 (en) * | 1994-08-29 | 1996-03-07 | Nippon Zeon Co., Ltd. | Unsaturated nitrile-conjugated diene copolymer, process for producing the same, and vulcanizable rubber composition |
US5703189A (en) * | 1994-08-29 | 1997-12-30 | Nippon Zeon Co., Ltd. | Unsaturated nitrile-conjugated diene copolymer, process for producing same and vulcanizable rubber composition |
US5807941A (en) * | 1994-08-29 | 1998-09-15 | Nippon Zeon Co., Ltd. | Unsaturated nitrile-conjugated diene copolymer process for producing same and vulcanizable rubber composition |
JP2012007172A (en) * | 2011-08-15 | 2012-01-12 | Asahi Kasei Chemicals Corp | Copolymer latex and composition for paper coating |
Also Published As
Publication number | Publication date |
---|---|
JP2933985B2 (en) | 1999-08-16 |
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