CN1059342A - The method for preparing cationic polymeric dispersion - Google Patents
The method for preparing cationic polymeric dispersion Download PDFInfo
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- CN1059342A CN1059342A CN91108599A CN91108599A CN1059342A CN 1059342 A CN1059342 A CN 1059342A CN 91108599 A CN91108599 A CN 91108599A CN 91108599 A CN91108599 A CN 91108599A CN 1059342 A CN1059342 A CN 1059342A
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- ethylene copolymer
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- dispersion
- quaternary salt
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- 239000006185 dispersion Substances 0.000 title claims abstract description 112
- 125000002091 cationic group Chemical group 0.000 title claims description 24
- 238000000034 method Methods 0.000 title abstract description 30
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003839 salts Chemical group 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000007259 addition reaction Methods 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- -1 forms Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 22
- 239000004065 semiconductor Substances 0.000 claims description 22
- 238000003384 imaging method Methods 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims 4
- 230000008018 melting Effects 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229920006317 cationic polymer Polymers 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 82
- 239000000463 material Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 235000011167 hydrochloric acid Nutrition 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000004513 sizing Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229920006322 acrylamide copolymer Polymers 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 238000005956 quaternization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 229940040145 liniment Drugs 0.000 description 2
- 239000000865 liniment Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- WZISPVCKWGNITO-UHFFFAOYSA-N 4-(diethylamino)-2-methylidenebutanamide Chemical compound CCN(CC)CCC(=C)C(N)=O WZISPVCKWGNITO-UHFFFAOYSA-N 0.000 description 1
- RINDUYMVZWQJDB-UHFFFAOYSA-N 4-amino-2-methylidenebutanamide Chemical compound NCCC(=C)C(N)=O RINDUYMVZWQJDB-UHFFFAOYSA-N 0.000 description 1
- XZQWWHBLXRBQKI-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanoic acid Chemical compound CN(C)CCCC(=C)C(O)=O XZQWWHBLXRBQKI-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- DNWSSZXZTVMPKC-UHFFFAOYSA-N n,n-dihydroxypropan-1-amine Chemical compound CCCN(O)O DNWSSZXZTVMPKC-UHFFFAOYSA-N 0.000 description 1
- FZLUWDXMHJPGBS-UHFFFAOYSA-N n-(3-aminopropyl)prop-2-enamide Chemical compound NCCCNC(=O)C=C FZLUWDXMHJPGBS-UHFFFAOYSA-N 0.000 description 1
- DCBBWYIVFRLKCD-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]-2-methylprop-2-enamide Chemical compound CN(C)CCNC(=O)C(C)=C DCBBWYIVFRLKCD-UHFFFAOYSA-N 0.000 description 1
- CKIBIKFBPKFOQX-UHFFFAOYSA-N n-butyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCCCN(N(C)C)C(=O)C=C CKIBIKFBPKFOQX-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
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- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本文披露了一种阳离子聚合物的水分散体的制 备方法，该分散体可通过一种乙烯共聚物与盐酸水溶 液反应生成的季盐与一种表卤代醇进行加成反应来 制得，其中乙烯共聚物含40％至80％(重量)乙烯和 20至60％(重量)至少一种由式(I)所示的氨烷基丙 烯酰胺共聚单体。式中R1代表氢原子或甲基，R2和 R3各自代表氢原子或含1至4个碳原子的烷基；而 n代表2至4的整数，按照日本工业标准K-6760测 定的乙烯共聚物的熔融指数为10至1000克/10分 钟。
This paper discloses a method for preparing an aqueous dispersion of a cationic polymer, which can be prepared by an addition reaction of a quaternary salt formed by the reaction of an ethylene copolymer with an aqueous solution of hydrochloric acid and an epihalohydrin, wherein The ethylene copolymers contain 40 to 80% by weight of ethylene and 20 to 60% by weight of at least one aminoalkylacrylamide comonomer represented by formula (I). In the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 each represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms; and n represents an integer from 2 to 4, measured according to Japanese Industrial Standard K-6760 The melt index of the ethylene copolymer is from 10 to 1000 g/10 minutes.
Description
The invention relates to a kind of method of water dispersion of the cationic polymers from the preparation of novel ethylene copolymer.
The water dispersion of cationic polymers of the present invention is used to form the antistatic or semi-conductor of a kind of softish and waterproof and films.This filming can be by with this water dispersion dipping or apply a matrix, for example paper and plastics film and dry and form.
In a kind of important use, cationic polymeric dispersion of the present invention is coated to a kind of electric imaging record series of strata, wherein on electric imaging recording materials, form latent image by electric signal, described electric imaging recording materials include the carrier of an electrical isolation, one conductive layer and a recording layer are arranged on it in order, and set has a kind of charged toning agent powder to obtain visible image above it.In this application, aqueous polymer dispersion of the present invention can be used from conductive layer so that the electric imaging recording materials with good film characteristics and writing function to be provided individually or with a kind of metal-oxide semiconductor (MOS) one.
In another kind was used, cationic polymeric dispersion of the present invention was useful as the additive in the papermaking.In more detail, in the forming process of sheet material, water dispersion of the present invention can add under neutrality or the alkaline condition with colloidality and wet tenacity on improving, thereby is applicable to production paper container, waterproof enhanced gauffered board or the like.In addition, cationic polymeric dispersion of the present invention is hopeful to utilize it to reduce the effect of surface resistivity or volume specific resistance and is applied to dustproof paper, IC(unicircuit) wrapping paper of parts or the like; Utilize its heat-sealing ability to be applied on the heat seal paper or the like; And the characteristic of utilizing its set dyestuff or pigment is applied on the painted matrix that laminated decorative sheet and coating paper use.
Proposed several aqueous polymer dispersions as conductive agent or static inhibitor, carried out drying then with these water dispersion dippings or coating insulating body (for example paper and plastics film).In these water dispersions, a kind of water dispersion of known cationic styrene polymkeric substance becomes quaternary salt to obtain by making chloromethylated polystyrene with a kind of reactive tertiary amine, and this has description in as Japanese patent laid-open publication gazette 7871/73 and 34150/74.But,,, surface conductivity is caused detrimentally affect in the preservation process so matrix is easy to curl or film be easy to break owing to applying cationic styrene polymkeric substance and the dry shortage flexibility of filming that forms on the paper or on the plastics film.
Be used at cationic polymers under the situation of conductive layer of electric imaging recording materials, described polymkeric substance mixes with a kind of metal-oxide semiconductor (MOS) etc., so that improve electroconductibility and reduce the dependency of surface resistivity to humidity, this has introduction (term " OPI " refers to " not examining disclosed Japanese patent application " here) in as Japanese patent application (OPI) 9524/80 and 331/80.In this respect, when independent use cationic styrene polymkeric substance, it is not enough to the receptivity of mineral filler.Consider that from the stability of record video under low wet atmosphere the receptivity of metal-oxide semiconductor (MOS) is had special importance.
On the other hand, the water dispersion of known cationic polymers by ethylene copolymer preparation includes and a kind ofly reacts the water dispersion that obtains by the multipolymer and a kind of acid that make ethylene/acrylic acid aminoalkyl ester cpds in water, and this introduces in Japanese patent application (OPI) 16542/72.This water dispersion is good for the receptivity of mineral filler such as metal-oxide semiconductor (MOS) (for example zinc oxide, stannic oxide, titanium oxide etc.), after it is coated on the last also drying of matrix (as paper and plastics film), provide one deck semi-conductor not only soft but also water-fast or solvent to film.Although formed the filming of water dispersion by the copolymer of ethylene/acrylic acid aminoalkyl ester cpds has these advantages, compare with filming of cationic styrene polymkeric substance, the former has higher surface resistivity.Water dispersion on this conductive layer that is coated to the electric record material does not reach enough writing functions, thereby uses in practice as yet.
Form the field at sheet material, disclosed series of strata are noticeable in the Japanese patent application (OPI) 98304/83 and 180697/83.According to these series of strata, in water, react and generate quaternary salt and then make it and show fontanel and carry out the water dispersion that addition reaction obtains by in aqueous pulp material, adding a kind of multipolymer by making ethylene/acrylic acid aminoalkyl ester cpds and various organic or inorganic acid, can improve upward colloidality and wet tenacity simultaneously for alcohol.
The inventor studies the practical application of above-mentioned technology.Yet, the water dispersion that makes owing to the multipolymer from ethylene/acrylic acid aminoalkyl ester cpds should add so that bring about the desired effect with sizable amount, so, compare with the general series of strata that tackiness agent and wet strength agent use, from the viewpoint of economy, the result who obtains is not gratifying for practical application.
Therefore, required to solve the incident variety of issue of water dispersion that makes with traditional multipolymer from ethylene/acrylic acid aminoalkyl ester cpds, the electroconductibility of filming that promptly obtains is not enough; The function of colloidality and wet tenacity is not enough on giving simultaneously in sheet material forms.
In sum, an object of the present invention is to provide a kind of water dispersion of the cationic polymers that makes from ethylene copolymer, from function and economic viewpoint, it has actual benefit as the conductive layer of electric imaging recording materials or the additive of paper grade (stock).
According to the extensive studies result, found from the cationic polymeric dispersion that the novel multipolymer of ethene and aminoalkyl acrylamide comonomer makes compare with traditional cationic polymeric dispersion demonstrate form conducting coating characteristic be improved significantly, and make colloidality and wet tenacity generation significantly improve effect simultaneously.
In first embodiment of the present invention, a kind of water dispersion of cationic polymers is provided, it is by making a kind of 40～80%(weight that contains) ethene and 20～60%(weight) the ethylene copolymer of at least a aminoalkyl acrylamide comonomer and hydrochloric acid in water, react to form quaternary salt, by addition reaction the quaternary salt that obtains and a kind of fontanel of showing are obtained for the alkylol cpd reaction then, the following formula I of described comonomer represents and has 10～1000 to restrain/10 minutes melt index (according to the method mensuration of JIS K-6760).
Formula I is expressed as
R in the formula
1Represent a hydrogen atom or a methyl; R
2And R
3Each represents a hydrogen atom or the alkyl with 1～4 carbon atom; N is an integer of 2～4.
In second embodiment of the present invention, improved a kind of by in above-mentioned cationic aqueous polymer dispersion, adding a kind of alcohol amine compound, heat-treating the water dispersion of the cationic polymers that obtains then.
At first, according to water dispersion of the present invention, it is characterized in that only having excellent absorption ability, and be the flexibility of filming that forms thus, eliminated hidden danger such as problems such as curling of film rhegma or matrix to mineral filler such as metal-oxide semiconductor (MOS); And filming of forming thus has gratifying water tolerance and solvent resistance, so, compare in practicality more reliable with the water dispersion of commercially available cationic styrene polymkeric substance.Moreover, the water dispersion of first embodiment provides superior filming, and its surface resistivity is far below the surface resistivity of filming that traditional cationic polymeric dispersion obtained that makes by the multipolymer from ethylene/acrylic acid aminoalkyl ester cpds.
Secondly,, it is characterized in that comparing the obvious behavior of going up colloidality and wet tenacity simultaneously that improved, so just can reach ideal efficacy levels in the practical application with the additive of decrement with the water dispersion of aforementioned conventional according to water dispersion of the present invention.
The preparation that can be used as the ethylene copolymer of raw material can be by radical polymerization 40～80%(weight under High Temperature High Pressure), 50～75%(weight preferably) ethene and 20～60%(weight), 25～50%(weight preferably) the represented aminoalkyl acrylamide comonomer of at least a formula I realize.
If the content of the chain link of the aminoalkyl acrylamide comonomer in the ethylene copolymer is lower than 20%(weight), the content that is to say the ethene chain link is higher than 80%(weight), then quaternary salt and table fontanel may have very poor wetting ability for the product that the addition reaction between the alkylol cpd obtains, and can not provide to contain all fine grain stable water dispersion.On the other hand, if the content of ethene chain link is lower than 40%(weight), that is to say that the content of aminoalkyl acrylamide comonomer chain link surpasses 60%(weight), the water dispersion that then obtains only forms and is not enough to water-fast and low excessively the filming of film toughness.When such film during as the conductive layer of electric imaging recording materials, writing with pencil or garden pearl pen to be impossible, that is to say when such water dispersion is used as the additive of paper, for last colloidality to improve effect not enough.
The viewpoint of the physicals of filming, the particularly film strength that forms from the viscosity of water dispersion with by this water dispersion is used for ethylene copolymer of the present invention and should has 10～1000 grams/10 minutes.Preferably 30～500 restrain/10 minutes melt index (measuring) according to JIS K6760.
According to above-mentioned for example Japanese patent laid-open publication gazette 22523/67 and 5194/78 method, above-mentioned ethylene copolymer can be by the preparation of high-pressure free radical polyreaction.More particularly, the aminoalkyl acrylamide compound of ethene and formula I is fed a vessel type reactor of being furnished with agitator or barrel reactor continuously with a kind of free radical catalyst such as oxygen, organo-peroxide, azo-compound etc. so that under the temperature of the pressure of 500～3000kg/cm and 100～300 ℃, carry out polymerization.Can use various types of chain-transfer agents, for example ethane, propane, propylene etc. are to adjust the molecular weight of polymkeric substance.
The object lesson that can be used for the aminoalkyl acrylamide comonomer of recommendation of the present invention has dimethylaminoethyl acrylamide, dimethyl aminopropyl acrylamide, dimethylamino butyl acrylamide, diethyl aminoethyl acrylamide, diethyl amino propyl group acrylamide, diethyl amino butyl acrylamide, di aminoethyl acrylamide, di aminopropyl acrylamide, N-(1, the corresponding methacrylamide derivatives of acrylamide or the like 1-dimethyl-3-dimethyl aminopropyl), and these acrylamide derivatives.These aminoalkyl acrylamide comonomers both can use separately.Also can two or more combine use.
In the comonomer of enumerating in the above, what recommended most is dimethyl aminopropyl acrylamide, dimethyl aminopropyl Methacrylamide, dimethylaminoethyl acrylamide and dimethylaminoethyl Methacrylamide.
In order to improve the pliability of filming that forms by this water dispersion or to reduce heat-sealing temperature, ethylene copolymer also can include one or more comonomers except that ethene and aminoalkyl acrylamide compound, for example methyl acrylate, methyl methacrylate, ethyl propenoate, n-butyl acrylate, vinyl acetate, propionate, dimethylaminoethyl acrylate methyl base aminoethyl ester, vinylformic acid dimethylaminoethyl ester or the like, its ratio can be up to 20%(weight).
The amount of hydrochloric acid that is used for the ethylene copolymer quaternization is between the ethylene copolymer of per 100 parts (moles) amino 50～200 parts, preferably 80～150 parts (mole).If the consumption of hydrochloric acid is lower than 50 parts, the quaternary salt that then obtains often has very poor wetting ability, and the adduct that obtains for alkylol cpd reaction with the table fontanel subsequently can not provide the stable and low viscous all fine grain water dispersion that contains.On the other hand, if the consumption of hydrochloric acid surpasses 200 parts, the water dispersion that obtains thus forms films that often water tolerance and film strength are not enough.
In general; be pill or pulverous ethylene copolymer and hydrochloric acid and under 60～100 ℃ and barometric point, mixture stirred 30～120 minutes by in the water of 100 weight parts, adding 5～35 weight parts, can fully finish the quaternization of hydrochloric acid and ethylene copolymer and react.In some cases, ethylene copolymer still keeps its shape in the quaternization reaction process, just with the aqueous hydrochloric acid swelling.This carrier because becoming for the addition reaction of alkylol cpd by follow-up and table fontanel, reaction system a kind ofly contains all fine grain water dispersion, so can not have problems.
Then, spirit of salt quaternary salt and a kind of table fontanel of the ethylene copolymer that obtains thus carried out addition reaction for alkylol cpd, thereby form a kind of even and stable water dispersion.
The table fontanel that participates in reaction comprises Epicholorohydrin, epibromohydrin or the like for alcohol, and particularly best with Epicholorohydrin.According to the amino meter of per 100 parts (moles) contained in the ethylene copolymer, the table fontanel is 50～200 parts (moles), preferably 80～150 parts (mole) for the consumption of alcohol.When the table fontanel is lower than 50 parts for the consumption of alkylol cpd, can not obtain the stable and low viscous all fine grain water dispersion that contains; If its consumption surpasses 200 parts, the water dispersion that obtains only forms can not be fully water-fast and low the filming of film strength, caused the problem in the actual use.
With the table fontanel for the alkylol cpd addition reaction generally can 20～100 ℃, be preferably in 40～90 ℃ and stir under carried out 30～300 minutes.The his-and-hers watches fontanel is not specifically limited for the feeding manner of alkylol cpd, and it can just all drop at the beginning, or continuously, or drop into intermittently.
If need, the cationic polymeric dispersion of the present invention that makes thus can have a kind of alcohol amine compound in the presence of heat-treat.What the surface resistivity that provides the water dispersion that obtains by this heat treating method was further reduced films.
Used alcohol amine compound comprise thanomin, diethanolamine, trolamine, Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, dihydroxy-propylamine, two (dihydroxypropyl) amine, three (dihydroxypropyl) amine, or the like.In addition, can also use the polyamines-polyhydroxy-alcohol compound that obtains by the reaction of alkylene oxide and polyamines, for example the adduct of the adduct of oxyethane (4 moles) and quadrol, oxyethane (4 moles) and propylene diamine etc.In the middle of these alcohol amine compounds, best is diethanolamine.
In per 100 parts (moles) amino of existing in the ethylene copolymer is benchmark, and the add-on of alcohol amine compound is 20 to 200 parts (mole), and is good with 50 to 150 parts (mole).Add-on is lower than 20 parts and is not enough to produce the effect that the surface resistivity of filming that the desirable water dispersion that makes gained makes reduces.On the other hand, if the consumption of alcohol amine compound surpasses 200 parts, then since in the resulting water dispersion excessive compound have neither part nor lot in reaction, what make thus films not only evenly but also is hygroscopic, the result causes the humidity dependency of surface resistivity to rise.
Generally carry out (being advisable with 40 to 100 ℃) under temperature is 20 to 100 ℃ condition with the reaction of alcohol amine compound, the reaction times is 1 to 10 hour.
The solid content of cationic polymeric dispersion of the present invention is preferably in per 100 parts of (weight) water 5 to 50 parts (weight), and 10 to 40 parts (weight) is better.Said herein " solid content " is meant the content that removes the afterwards remaining non-volatile substance that anhydrates by exsiccant method in about 100 ℃ of warm airs in water dispersion.Solid content surpasses 50 parts water dispersion owing to viscosity does not have flowability and its property used (as the performance that applies) poor too greatly on matrix.From the angle of production efficiency, transportation, selling price and the load of coating after drying, it also is worthless that solid content is lower than 5 parts water dispersion.
In film-forming process, this water dispersion is applied on the matrix (as paper and plastic film), and under about 50 ℃ to 150 ℃ condition heat drying.
When with water dispersion of the present invention during as the conductive layer of electric imaging recording materials, it can be mixed mutually with metal-oxide semiconductor (MOS), for example can mix with zinc oxide, Red copper oxide, Indium sesquioxide, stannic oxide, titanium oxide, cobalt oxide, nickel oxide, tantalum pentoxide, Vanadium Pentoxide in FLAKES, tungstic oxide, molybdic oxide etc. or these metal oxides that are mixed with doping agent.Being used in combination these metal oxide semiconductor materials can further reduce the surface resistivity of resulting conductive layer effectively and reduce the dependency of recording density to humidity.
In order to make acrylic resin, vinyl chloride resin, butyral resin etc. have writing quality, sign performance or natural materials sensation, usually with the coating of the pigment (as titanium oxide, lime carbonate, starch, clay etc.) that wherein contains the microparticle shape as the dielectric layer resin solution that imposes on the semiconductor laminated sheet material (the exsiccant method makes by water dispersion of the present invention being coated on paper or the plastic film then).The thickness of this class coating is about 5 to 10 microns (dry state).Its surface resistivity is preferably about 10 under normal temperature and normal atmosphere
12To 10
15Ω (ohm).
Also can add additive, for example dyestuff, pigment, stopping composition, tensio-active agent, static inhibitor, softening agent, lubricant, dispersion agent, defoamer etc., and water soluble resin, for example polyvinyl alcohol as required in the water dispersion of the present invention.
According to the present invention, can obtain by water dispersion being coated to subsequent drying on paper or the plastic film that one deck is thin, transparent, the filming of soft and tough.Dried coating is non-water-soluble, and moist and water are had goodish stability.Like this, the recording density that contains the electric imaging recording materials of water dispersion of the present invention in the conductive layer be subjected to the little and record performance of the influence of humidity not in time passing and change.When with this water dispersion during as static inhibitor, resulting film has persistent antistatic property.
In addition, in the sheet material forming process, use water dispersion of the present invention the gluing performance and the wet tenacity of paper are significantly improved as additive.Both water dispersion can have been joined as wet side effect (wet end) additive in this class is used also to make it be impregnated in the paper in the paper pulp.In the previous case, generally being that the cationic polymers that is scattered in the water is joined in the paper pulp by the consumption of per 100 parts of paper pulp (dry state weight) 0.1 to 5 part (weight), is the paper that forms that heating several seconds to several minutes makes its drying under 70 to 150 ℃ the condition in temperature then.In this case, can be used in combination water tank and scold agent, as wax, polysiloxane and fluorocarbon resin etc.
Introduce the present invention in more detail by following embodiment more now, still it should be noted and to think that the present invention only limits to the content of embodiment.In these embodiments, all percentage, ratio (unless otherwise indicated) all by weight.
Embodiment 1
With 360 gram water, 100 gram ethene/dimethylaminopropyl acrylamide ratios is that 59: 41 and melt index are that the ethene/dimethylaminopropyl acrylamide copolymer particle and 27 36% aqueous hydrochloric acids that restrain of 300 grams/10 minutes (press JIS K-6760 and measure, be hereinafter identical) join in 1000 milliliters of volumetrical glass flask.Add the hydrochloric acid be equivalent to per 100 parts (moles) (in multipolymer) amino 100 parts (moles).Under stirring condition mixture was heated up 30 minutes to 100 ℃ from room temperature, also under refluxad continue to stir 60 minutes under this temperature, the result is that particle disappears, and obtains the heavy-gravity water slurry.
Under stirring condition, be cooled to after 80 ℃, within 30 minutes, in water slurry, splash into 24 gram (be equivalent to per 100 parts of (mole) amino have added 100 parts (moles) in the multipolymer) Epicholorohydrins.Under 80 ℃ of conditions, continue then to stir 270 minutes, obtain the even water dispersion of light brown.Resulting water dispersion is called dispersion A-1.Under 25 ℃ of conditions, the pH value of dispersion A-1 is 5.6, and viscosity is 49 centipoises.The granularity of dispersive polymer beads is 0.1 micron or littler.The solid content of dispersion A-1 (defining the same) is 26%.
Embodiment 2
Under 80 ℃ and stirring condition, in 1000 milliliters of volumetrical glass flask, add dispersion A-1,28 gram (being equivalent to 100 parts (moles), is 100 parts (moles) in the amino in the multipolymer) diethanolamine of preparing among the 490 gram embodiment 1.Under this temperature, continue to stir 300 minutes, cool off then, obtain the even water dispersion of light brown.The dispersion that obtains is called dispersion A-2.Under 25 ℃ of conditions, the pH value of dispersion A-2 is 6.9, and viscosity is 17 centipoises, and solid content is 30%.The granularity of dispersive polymer beads is 0.1 micron or littler.
Embodiment 3 to 8
Prepare dispersion A-3 to A-8 by the method identical with embodiment 1 or 2, different is has replaced ethene/dimethylaminopropyl acrylamide copolymer of using among the embodiment 1 or 2 with various ethene copolymers (having listed composition and melt index separately in the table 1) particle.A-3 to A-8 contains the stable low viscosity water dispersion that granularity is 1 micron or littler polymer beads.
Reference example 1 to 3
In order to estimate the performance of water dispersion of the present invention the time as electrically conducting coating or additive for paper making, prepared contrast water dispersion R-1 to R-3 by the method identical with embodiment 1 or 2, different is to have replaced ethene/dimethylaminopropyl acrylamide copolymer with the multipolymer of being made up of ethene and a kind of vinylformic acid aminoalkyl comonomer listed in the table 1.All dispersion R-1 to R-3 dispersion performances are all similar to the water dispersion performance that makes by example 1 or example 2, that is to say that its viscosity is low, and the particulate granularity is 1 micron or littler.
Reference example 4
With 1.3 times of (mole) hydrochloric acid make with example 5 in the same ethene copolymer (dimethylaminopropyl acrylamide content 50%) used quaternized, preparing solid content by the method identical with embodiment 1 is 24% quaternary salt.Product is heavy-gravity water slurry shape solid one liquid mixture.Compare with embodiment 5, for the stable aqueous dispersions that obtains containing microparticle obviously should add Epicholorohydrin subsequently.
Reference example 5 and 6
Press the method operation of embodiment 1 or 2, the dimethylaminopropyl acrylic acid content of different the is ethene copolymer of initial usefulness is 15%, melt index is 100 grams/10 minutes, but because copolymer pellet can not completely dissolve, thereby fail to obtain uniform water dispersion.
Annotate: 1) dimethylaminopropyl acrylamide
2) dimethylaminopropyl MAAm
3) dimethylaminoethyl methacrylate
4) vinylformic acid dimethylamino ethyl ester
5) diethanolamine
6) monoethanolamine
Embodiment 9
With rod coater #10 the dispersion A-2 by embodiment 2 preparation be applied to quantitatively be 84 grams/square metre nothing wood paper on, and on the hot air circulate drying machine in 100 ℃ of dryings 5 minutes, obtain not having the paper that curling (Curling-free) applied, have on it one deck dry weight be 1.2 the gram/square metre uniform semi-conductivity film.
With resistance instrument (the superinsulation instrument of making by Toa Derpa Kogyo K.K., SM-10 E type) be in temperature that 23 ℃, relative humidity (RH) are 30%, 50%, 70%, voltage is the surface resistivity of measuring the coated surfaces of this paper under 100 volts the condition, as shown in table 2, measured value is respectively 5 * 10
7Ohm, 8 * 10
6Ohm, 9 * 10
5Ohm.In relative temperature be under 50% the condition before the coating surface resistivity of paper be 4 * 10
13Ohm.
70: 30 ratios are Liniment of a kind of manufacturing dielectric layer " C " (methyl ethyl ketone solution of vinyl acetate/vinylchlorid/vinyl alcohol ter-polymer resin that Sakata Shokai K.K. makes, solid content 28%) and " Softon by weight
1800 " (the registrar name of an article of the calcium carbonate fine powder that Bihoku Funka Kogyo K.K. makes, 1.25 microns of mean particle sizes) mixes mutually to prepare a kind of dispersion.With rod coater #10 prepared dispersion is coated on the semi-conductivity film of paper of above-mentioned coating, undertaken air-dry by gas blower, and in circulating hot air dryer in 100 ℃ of dryings 5 minutes, obtain the coating gross dry weight and be 6.0 grams/square metre electric imaging recording paper.
Electricity consumption imaging record tester (the AO type electricity imaging plotting apparatus EP101 that Matsushita Denso K.K. makes) is under 30% the condition prepared electric imaging recording paper to be carried out the test of electric imaging record in relative humidity, can obtain gem-pure recording geometry.
Embodiment 10 to 13
Have the paper that one deck is even and glossiness nothing of filming is curled and applied by the method manufacturing identical with embodiment 9, different is to use embodiment 3,4 respectively, and dispersion A-3, the A-4, A-5 or the A-7 that make in 5 or 7 have replaced dispersion A-2.As shown in table 2, the surface resistivity of resulting each paper that applied has all reached gratifying level.
By the method identical this paper that applied is coated one dielectric layer again, obtain electric imaging recording paper with embodiment 9.The various recording papers that obtain all have fabulous record effect.
Comparative example 1 and 2
Method by example 9 prepares the paper that applied, and different is to have replaced dispersion A-2 with the dispersion R-2 or the R-3 that prepare in reference example 2 or 3 respectively.As shown in table 2, the surface resistivity of the paper of prepared coating is higher.Like this, poor with the record effect of these electric imaging recording papers of making by the paper of the coating of the method manufacturing identical with embodiment 9, only obtain unsharp generally pattern, the some of them point disappears.
By above as can be known, with compare with the water dispersion of ethylene/acrylic acid aminoalkyl ester copolymer, water dispersion with the copolymer of ethene of the present invention/aminoalkyl group acrylamide compound can obtain having filming of high electrical conductivity, thereby can obtain the electric preferably imaging recording paper of effect.
Embodiment 14
(Honjo Chemecal K.K. makes to add the Powdered electroconductive zinc oxide of 25 grams among the 100 gram dispersion A-1 that make in embodiment 1,1.5 microns of mean particle sizes, see Japanese Patent 1,029,615 and 1,029, No. 616), and with mixture in stirring at room 30 minutes, obtain wherein being distributed with equably the gray mixture of Zinc oxide particles.With rod coater #10 with the gained mixture be coated in quantitatively be 84 grams/square metre nothing wood paper on, and in 110 ℃ warm air dry 3 minutes, obtain having on it one deck dry weight be 7.6 grams/square metre the paper of the even white coating of filming.Under the condition identical, measure the surface resistivity of this paper that applied, be respectively in relative humidity that measurement result is respectively 2 * 10 under 30,50 and 70% the condition with embodiment 9
6, 7 * 10
5With 5 * 10
5Ohm, the resistivity of the paper that this explanation applied is lower, and less to the dependency of humidity.
Under stirring condition, Liniment (the toluene solution of the acrylic resin that Nagase Kasei Kogyo K.K. makes that 100 grams is used to prepare dielectric layer " 50C ", solid content 50%), 50 grams among the embodiment 9 used same lime carbonate and 180 gram toluene mix mutually, prepare a kind of uniform dispersion separately.With rod coater #10 this dispersion is coated with on the paper of the coating of preparing in front, and in 110 ℃ warm air dry 5 minutes, obtain total coating dry weight and be 13.1 grams/square metre electric imaging recording paper.
When under the condition identical, carrying out electric imaging record test, obtain recording figure forming very clearly, without any the phenomenon of a disappearance with embodiment 9.
Embodiment 15
Mica " MEC-500 " (the Teikoku Kako K.K. manufacturing that in the dispersion A-5 that 100 grams make by embodiment 5, adds flaky, the transparent electroconductibility of 18 grams, the mean particle size of mica particles is that 10 microns, specific surface are 19 meters squared per gram, scribble stannic oxide and weisspiessglanz on it), under room temperature, stirred 30 minutes subsequently, wherein be evenly distributed with the gray mixture of mica particles.With rod coater #10 this mixture is coated on the surface that the corona treatment of the polyethylene terephthalate film " E-5101 " (manufacturing of Toyobo company limited) of one 75 micron thickness crosses, and in 120 ℃ warm air dry 2 minutes, obtain having one deck dry weight and be 8.5 grams/square metre, the stack membrane of filming glossiness, transparent, that binding property is very high.Measure by the method identical with embodiment 9, be respectively in relative humidity under 30,50 and 70% the condition, this surface resistivity of filming is respectively 9 * 10
5, 5 * 10
5With 3 * 10
5Ohm.This resistivity that this stack membrane is described is lower, and less to the dependency of humidity.
Adopt the method identical on laminated film, to form a dielectric layer, thereby obtain to be used for the semitransparent layer press mold that telecommunication is write down with embodiment 14, on this film the dry gross weight of coating be 14.7 restrain/square metre, its mist degree is 76%.With embodiment 9 the same terms under carry out telecommunication record test, consequently obtain a kind of very clear pattern that does not have any some extinction tests.
Embodiment 16 to 18
The dispersion A-1 that consumption is as shown in table 3, it is that 410 milliliters and N-BKP/L-BKP ratio are that 1/1 concentration is in 1.0% the pulp slurry that A-5 or A-7 add to a kind of its Canadian standard fluid rate of discharge, with 200 rev/mins rotating speed this is mixed then and stirs 2 minutes.By means of TAPPI standard tabletting machine above-mentioned slurry is laminated, and in 110 ℃ of down dry regular hours (1 or 10 minute), just can to obtain quantitatively be 80 grams/square metre paper.Wet length of fracture and degree of sizing thereof as the wet tenacity judgement criteria of this paper can be measured as follows, and it the results are shown in table 3.
1) degree of sizing:
Be under 65% the condition according to St in 25 ℃ and relative humidity
The ckigt method is measured.
2) wet length of fracture (measuring) according to the P8113 of Japanese Industrial Standards
Under 20 ℃, place the water dipping after 60 minutes on paper, measure its wet tensile (strength), just can calculate wet length of fracture according to this measurement result and following equation:
Wet length of fracture (km)=(tensile strength that records (kilogram) * 1000)/(specimen width (millimeter) * quantitatively (gram/square metre))
Comparative example 3 and 4
Adopt the method identical with embodiment 16 to 18 to prepare the paper sample, different is to replace water dispersion of the present invention with the dispersion R-1 or the R-2 that prepare in reference example 1 or 2.Adopt the method identical with embodiment 16 to 18 to measure the degree of sizing of paper and the length of fracture that wets, gained the results are shown in table 3.
Compare with the result of embodiment 16 to 18, obviously, water dispersion of the present invention can improve degree of sizing and wet tenacity more effectively than the prepared water dispersion of multipolymer by ethylene/acrylic acid aminoalkyl ester cpds.
The comparative example 5
Adopt the method identical with embodiment 16 to 18 to prepare the paper sample, different is usefulness " Sumirez resin
#675 " (polymeric amide-Epicholorohydrin type wet-strength resins that Sumitomo chemistry company limited generates; Content is 25% the aqueous solution) replace water dispersion of the present invention.Adopt the method identical with embodiment 16 to 18 to measure degree of sizing and the length of fracture that wets, its result is in table 3.Table 3 shows, adds wet strengthening resin and can not produce any gluing effect.
Embodiment 19 and 20
With quantitatively be 80 grams/square metre hand-built not sized paper (30 centimetres of 10 cm x) impregnated in (result of dilution makes polymer concentration reach numerical value shown in the following table 4) among 500 milliliters of diluted dispersion A-5 or A-8, in 110 ℃ warm air dry 5 minutes then.In the weight of sized paper not is that the polymer recovery of benchmark is shown in table 4.Adopt the method identical with embodiment 16 to 18 to measure the degree of sizing of impregnated paper and the length of fracture that wets, measurement result is shown in table 4.Table 4 has shown the influence of various factors to degree of sizing and wet tenacity generation.
Table 4
The embodiment sample polymer concentration polymer rate of recovery degree of sizing length of fracture that wets
Sequence number sequence number %(weight) %(weight) (second) (km)
19 A-5 0.1 0.1 41 0.79
1.0 1.1 92 2.58
2.0 2.4 102 3.73
20 A-8 0.1 0.1 45 0.71
1.0 1.2 97 2.42
2.0 2.7 105 3.57
Contrast does not have--0 0.24
Embodiment
As mentioned above, the water dispersion of the present invention that the multipolymer that is obtained by ethene and aminoalkyl acrylamide comonomer makes, when it being coated on matrix and through super-dry, can obtain the paint film that one deck electroconductibility is improved significantly, thereby, be enough to be used as just like the polymkeric substance that is applicable to telecommunication recording materials conducting stratum.
In addition, water dispersion of the present invention also can be used as wet side effect (wet end) additive or paper soaker and improves degree of sizing and wet tenacity simultaneously.
With reference to specific embodiments of the present invention and to the detailed description that the present invention did, various not deviate from essence of the present invention and do not exceed the improvement of the scope of the invention and revise all be conspicuous for the person skilled in art.
Claims (4)
1, a kind of semiconductor layer stampings of forming by matrix and the semiconductor film that on this matrix, forms, semiconductor film wherein is coated on matrix by the cationic polymeric dispersion that will obtain as follows and in 50 to 150 ℃ of these coatings of drying make: make the reaction of a kind of ethylene copolymer and aqueous hydrochloric acid generate a kind of quaternary salt, this quaternary salt and with the table fontanel carry out addition reaction for alkylol cpd, just can make above-mentioned cationic polymeric dispersion, above-mentioned ethylene copolymer contains the aminoalkyl acrylamide comonomer shown in 40 to 80% (weight) ethene and at least a molecule formula I of 20 to 60% (weight):
R in the formula
1Represent hydrogen atom or methyl; R
2And R
3Represent hydrogen atom separately or contain the alkyl of 1 to 4 carbon atom; And n represents 2 to 4 integer, and the melting index of this ethylene copolymer of measuring according to the K-6760 of Japanese Industrial Standards is 10 to 1000 grams/10 minutes.
2, a kind of semiconductor layer stampings of forming by matrix and the semiconductor film that on this matrix, forms, semiconductor film wherein is by being coated on a kind of cationic polymeric dispersion matrix and in 50 to 150 ℃ of these coatings of drying make, this cationic polymeric dispersion is preparation like this: make the reaction of a kind of ethylene copolymer and aqueous hydrochloric acid generate quaternary salt, this quaternary salt and carry out addition reaction for alkylol cpd, its adduct with a kind of table fontanel subsequently again with a kind of alcohol amine compound reaction; Above-mentioned ethylene copolymer contains 40 to 80%(weight) ethene and 20 to 60%(weight) at least a aminoalkyl acrylamide comonomer shown in the molecule formula I:
R in the formula
1Represent hydrogen atom or methyl, R
2And R
3Represent hydrogen atom separately or contain the alkyl of 1 to 4 carbon atom, n represents 2 to 4 integer, and the melting index of this ethylene copolymer of measuring according to the K-6760 of Japanese Industrial Standards is 10 to 1000 grams/10 minutes.
3, a kind of laminated product that is used for electric imaging record, the semiconductor layer that forms earlier of preface and the dielectric layer that then forms are formed successively by matrix and on this matrix, described semiconductor layer makes by a kind of cationic polymeric dispersion being coated on down dry these coatings of matrix and in 50 to 150 ℃, wherein cationic polymeric dispersion is like this preparation: make a kind of ethylene copolymer and aqueous hydrochloric acid reaction generation quaternary salt, this quaternary salt and carry out addition reaction for alkylol cpd with a kind of table fontanel; Above-mentioned ethylene copolymer contains 40 to 80%(weight) ethene and 20 to 60%(weight) at least a aminoalkyl acrylamide comonomer as molecule formula I institute formula:
R in the formula
1Represent hydrogen atom or methyl, R
2And R
3Represent hydrogen atom separately or contain the alkyl of 1 to 4 carbon atom; N is 2 to 4 integer, the melting index of this ethylene copolymer of measuring according to the K-6760 of Japanese Industrial Standards is 10 to 1000 grams/10 minutes, be coated on semiconductor layer by the resin solution that will be applicable to dielectric layer, in 50 to 150 ℃ of following dryings just obtain above-mentioned dielectric layer then.
4, a kind of laminated product that is used for electric imaging record, formed by matrix and semiconductor layer that on this matrix, forms earlier successively and the dielectric layer that the back forms, described semiconductor layer makes by a kind of cationic polymeric dispersion being coated on down dry these coatings of matrix and in 50 to 150 ℃, wherein cationic polymeric dispersion is preparation like this: make the reaction of a kind of ethylene copolymer and aqueous hydrochloric acid and the generation quaternary salt, this quaternary salt and carry out addition reaction for alkylol cpd with a kind of table fontanel, its adduct reacts with a kind of alcohol amine compound subsequently again, and above-mentioned ethylene copolymer contains 40 to 80%(weight) ethene and 20 to 60%(weight) at least a aminoalkyl acrylamide comonomer shown in the molecule formula I:
R in the formula
1Represent hydrogen by atom or methyl; R
2And R
3Representing hydrogen atom or carbon atom quantity separately is 1 to 4 alkyl; N is 2 to 4 integer, the melting index of the above-mentioned ethylene copolymer of measuring according to Japanese Industrial Standards is 10 to 1000 grams/10 minutes, be coated on semiconductor layer and in 50 to 150 ℃ of down dry these coatings by the resin solution that will be applicable to dielectric layer, just obtain above-mentioned dielectric layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP268900/86 | 1986-11-11 | ||
| JP26890086 | 1986-11-11 | ||
| CN87107768A CN1024670C (en) | 1986-11-11 | 1987-11-11 | Process for preparing aqueous cationic polymer dispersions |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107768A Division CN1024670C (en) | 1986-11-11 | 1987-11-11 | Process for preparing aqueous cationic polymer dispersions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1059342A true CN1059342A (en) | 1992-03-11 |
Family
ID=25742382
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108602 Expired - Fee Related CN1030785C (en) | 1986-11-11 | 1987-11-11 | Use of sized paper made by adding an aqueous dispersion of a cationic polymer |
| CN91108599A Pending CN1059342A (en) | 1986-11-11 | 1987-11-11 | The method for preparing cationic polymeric dispersion |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108602 Expired - Fee Related CN1030785C (en) | 1986-11-11 | 1987-11-11 | Use of sized paper made by adding an aqueous dispersion of a cationic polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1030785C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084345C (en) * | 1999-08-05 | 2002-05-08 | 石油勘探开发科学研究院油田化学研究所 | Process for preparing high-molecular cationic polymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006007001A1 (en) * | 2004-06-17 | 2006-01-19 | Kemira Oyj | Cationic polymers containing 2-mhydrocyethyl-methacrylic as promoters for asa sizing |
-
1987
- 1987-11-11 CN CN 91108602 patent/CN1030785C/en not_active Expired - Fee Related
- 1987-11-11 CN CN91108599A patent/CN1059342A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084345C (en) * | 1999-08-05 | 2002-05-08 | 石油勘探开发科学研究院油田化学研究所 | Process for preparing high-molecular cationic polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1059005A (en) | 1992-02-26 |
| CN1030785C (en) | 1996-01-24 |
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