NO127413B - - Google Patents
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- Publication number
- NO127413B NO127413B NO141369A NO141369A NO127413B NO 127413 B NO127413 B NO 127413B NO 141369 A NO141369 A NO 141369A NO 141369 A NO141369 A NO 141369A NO 127413 B NO127413 B NO 127413B
- Authority
- NO
- Norway
- Prior art keywords
- acid
- interpolymer
- carbon atoms
- acrylamide
- paper
- Prior art date
Links
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 52
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 45
- 239000004816 latex Substances 0.000 claims description 40
- 229920000126 latex Polymers 0.000 claims description 40
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 37
- 239000005977 Ethylene Substances 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- -1 acrylyl Chemical group 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 150000007513 acids Chemical class 0.000 claims description 17
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical class OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 15
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical class OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229920001897 terpolymer Polymers 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000001530 fumaric acid Chemical class 0.000 claims description 8
- 239000011976 maleic acid Chemical class 0.000 claims description 8
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical class FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical class OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229940018557 citraconic acid Drugs 0.000 claims description 6
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 229940047670 sodium acrylate Drugs 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 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 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 claims description 2
- 229940048053 acrylate Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000000123 paper Substances 0.000 description 48
- 239000000758 substrate Substances 0.000 description 15
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 14
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000011111 cardboard Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Chemical class 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229940091181 aconitic acid Drugs 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical class OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Chemical class OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- USQCUKQZXOWUDF-YWZLYKJASA-N 6-chloro-n-[(3s)-1-[(2s)-1-(4-methyl-5-oxo-1,4-diazepan-1-yl)-1-oxopropan-2-yl]-2-oxopyrrolidin-3-yl]naphthalene-2-sulfonamide Chemical compound O=C([C@@H](N1C([C@@H](NS(=O)(=O)C=2C=C3C=CC(Cl)=CC3=CC=2)CC1)=O)C)N1CCN(C)C(=O)CC1 USQCUKQZXOWUDF-YWZLYKJASA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940112822 chewing gum Drugs 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- FRKMZLXCWXPBOB-UHFFFAOYSA-N diazanium;2-methylidenebutanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(=C)C([O-])=O FRKMZLXCWXPBOB-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- DSTWFRCNXMNXTR-AATRIKPKSA-N dipropyl (e)-but-2-enedioate Chemical compound CCCOC(=O)\C=C\C(=O)OCCC DSTWFRCNXMNXTR-AATRIKPKSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- ZFRKEVMBGBIBGT-UHFFFAOYSA-N ethenyl benzenesulfonate Chemical compound C=COS(=O)(=O)C1=CC=CC=C1 ZFRKEVMBGBIBGT-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- JWHMNITWPQGHPL-UHFFFAOYSA-N n-(2-hydroxypropanoyl)-2-methylprop-2-enamide Chemical class CC(O)C(=O)NC(=O)C(C)=C JWHMNITWPQGHPL-UHFFFAOYSA-N 0.000 description 1
- RUSRUYULUAYXIP-UHFFFAOYSA-N n-acetylprop-2-enamide Chemical compound CC(=O)NC(=O)C=C RUSRUYULUAYXIP-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 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
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- JICVCSXXNQPZEZ-UHFFFAOYSA-N prop-2-enoyl 3-hydroxypropanoate Chemical compound OCCC(=O)OC(=O)C=C JICVCSXXNQPZEZ-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/08—Homopolymers or copolymers of vinylidene chloride
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
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Description
Fremgangsmåte for fremstilling av et . -. , belagt papir eller lignende. , . , ,". Procedure for producing a . -. , coated paper or similar. , . , , ".
Nærværende oppfinnelse vedrorer.en fremgangsmåte for fremstilling av et belagt papir med et overtrekk som består av 5 - 95 % poly-vinylidenkloridpolymer og fra 95 - 5 vekts-$ av en interpolymer. The present invention relates to a method for producing a coated paper with a coating consisting of 5-95% polyvinylidene chloride polymer and from 95-5% by weight of an interpolymer.
Mere spesielt vedrorer oppfinnelsen en.fremgangsmåte for fremstilling av overtrukne, fibrose substrater i ark- og rulLeform,. More particularly, the invention relates to a method for producing coated, fibrous substrates in sheet and roll form.
hvor substratet kan være papir,-. kartong, for formede papirbe-holdere, tekstiler eller andre fibrose materialer,. hvor overtrekket påføres fra en blandet emulsjon av.en polyvinylidenklorid-polymerlateks.og en interpolymerlateks av etylen, vinylklq- where the substrate can be paper, -. cardboard, for shaped paper containers, textiles or other fibrous materials. where the coating is applied from a mixed emulsion of a polyvinylidene chloride polymer latex and an interpolymer latex of ethylene, vinyl chloride
rid og akrylamid, med eller uten små mengder, av andre monomere.. rid and acrylamide, with or without small amounts of other monomers..
Kfr. kl. 55f-15/20 Cf. at 55f-15/20
fibrøse substrater", slik som papir, anvendes utstrakt til for-pakning. Papir har imidlertid' en meget dårlig motstandsevne mot inntrengning av vanndamp, gasser, oljer, oppløsningsmidler og iett..tor å forbedre sperreraotstandsevnen mot vanndamp har papir vært overtrukket med eh rekke stoffer. Det mest vanlige pa-pirovertrékk er voks. Skjønt det med voks overtrukne papir, har . god sperremotstandsevne mot vanndamp i jevn eller ikke-krøllet tilstand, har det dårlig motstandsevne efter at det er krøllet. Øyensynlig er sprøheten for voks så stor, at krølling forårsa-ker brudd og derfor gir mange områder gjennom hvilke vanndamp kan passere med liten eller ingen motstand.: Dessuten, voksovertrukket papir tjen&r ikke til å danne en hård slitesterk overflate . fibrous substrates", such as paper, are used extensively for packaging. Paper, however, has a very poor resistance to the penetration of water vapour, gases, oils, solvents and, in order to improve the barrier resistance against water vapour, paper has been coated with a number of substances. The most common paper pyro-overcoating is wax. Although wax-coated paper has good barrier resistance to water vapor in the smooth or uncurled state, it has poor resistance after it is curled. Apparently, the brittleness of wax is so great, that curling causes breakage and therefore provides many areas through which water vapor can pass with little or no resistance.: Also, wax-coated paper does not serve to form a hard durable surface.
Overtrekning av :papir med asfalt har også vært forsøkt,og skjønt god sperremotstandsevne mot vanndamp oppnåes, har det overtrukne papir liten motstandsevne eftér å være krøllet. Dessuten er asfalt et sort, giftig materiale, som begrenser dets anvendelse som paplrovertrekk, særlig innen næringsmiddelindustri-en. Dessuten er asfaltovertrekk gjenstand for forandringer med Coating paper with asphalt has also been tried, and although good barrier resistance to water vapor is achieved, the coated paper has little resistance after being crumpled. In addition, asphalt is a black, toxic material, which limits its use as a pavement covering, particularly in the food industry. In addition, asphalt overlays are subject to changes
hensyn til flyteegenskaper med variasjoner i temperatur. consideration of flow properties with variations in temperature.
Papir har også vært overtrukket med en film av polyetylen. Det resulterende polyetylen-overtrukne papir finnes å ha mindre.motstandsevne mot inntrengning av vanndamp enn voksovertrukket papir, når overtrekket undersøkes i flat eller jevn ukrøllet tilstand. Polyetylenovertrukket papir finnes å være et bedre sperre-materiale enn det voksovertrukne papir når dette er krøllet. Paper has also been coated with a film of polyethylene. The resulting polyethylene-coated paper is found to have less resistance to water vapor penetration than wax-coated paper when the coating is examined in a flat or uniform uncurled state. Polyethylene-coated paper is found to be a better barrier material than the wax-coated paper when this is curled.
Por å forbedre motstandsevnen mot fuktighet, olje, oppløsnings-midler og fett har papir vært behandlet méd polyvinylidenklo-rld. Den karakteristiske sprøhét for polyvinylidenklorid forår-saker svikt i overtrekkene når disse krølles. Forsøk på å forbedre denne begrensede fleksibilitet ved anvendelsen av plastl-fiseringsmidler og komonomere med polyvinylldenkloridet resulterer i nedsatt effektivitet med hensyn til sperreegenskapene mot vann. Den dårlige motstandsevne mot slag for polyvinylldenkloridet resulterer også i brudd av filmen under risning og krolling ved hoy hastighet. To improve resistance to moisture, oil, solvents and grease, paper has been treated with polyvinylidene chloride. The characteristic brittleness of polyvinylidene chloride causes failure of the covers when these are creased. Attempts to improve this limited flexibility by the use of plasticizers and comonomers with the polyvinylidene chloride result in reduced effectiveness with respect to water barrier properties. The poor impact resistance of the polyvinylidene chloride also results in breakage of the film during rippling and curling at high speed.
Plastif iserte. polyvinylklorid-polymere anvendes ved papirover-trekkspåforinger. Da polyvinylkloridet normalt er utvendig pla-stifisert oppstår et tap i motstandsevnen mot vann, olje, fett og opplosningsmidler som folge av ekstraksjonen og utsondringen av plastifiseringsmidlet. Nærværet av plastifiseringsmidler re-duserer også motstandsevnen mot gjennomgang av gasser og væsker . Plasticized. Polyvinyl chloride polymers are used in paper overcoat applications. As the polyvinyl chloride is normally externally plasticised, a loss in resistance to water, oil, grease and solvents occurs as a result of the extraction and excretion of the plasticising agent. The presence of plasticizers also reduces the resistance to the passage of gases and liquids.
Det har således blitt sterkt bnsket å finne frem til materialer som er anvendelige for å overtrekke fibrose substrater, som på sin side kan anvendes som forpakningsmaterialer, og som vil gi god sperremotstandsevne mot olje, fett, opplosningsmidler og It has thus been strongly desired to find materials which are applicable for coating fibrous substrates, which in turn can be used as packaging materials, and which will provide good barrier resistance against oil, grease, solvents and
vanndamp. water vapor.
Det er således et formål ved nærværende oppfinnelse å frem-skaffe en fremgangsmåte for fremstilling av belagt papir og lignende som vil. gi forbedrete egenskaper til dette, slik som gode sperreegenskaper mot olje, fett, opplosningsmidler og vanndamp. It is thus an object of the present invention to provide a method for the production of coated paper and the like which will. give improved properties to this, such as good barrier properties against oil, grease, solvents and water vapour.
I overensstemmelse med nærværende oppfinnelse er det funnet at foran angitte og andre formål oppnås ved å påfore et fibrost substrat en blandet emulsjon bestående av en polyvinylidenklorid-polymerlateks og en etylen/vinylklorid/akrylamid-interpolymerlateks av den type som beskrives nedenfor. In accordance with the present invention, it has been found that the above and other purposes are achieved by applying to a fibrous substrate a mixed emulsion consisting of a polyvinylidene chloride polymer latex and an ethylene/vinyl chloride/acrylamide interpolymer latex of the type described below.
Fremgangsmåten ifolge nærværende oppfinnelse karakteriseres ved at papiret påfores en blandet lateks av polyvinylidenkloridpolymer og interpolymer, fulgt av torking for å fjerne vannet, deretter sammensmelte polymerene ved varme til en kontinuerlig film, idet interpolymeren er fra gruppen bestående av (a) en interpolymer som inneholder fra 5 - 70 % etylen, fra 30 - 95 % vinylklorid og fra 0,1 - 10 % av minst en annen polar monomer omfattende minst 0,1 - 10 % akrylamid, og resten av det polare monomerinnhold er fra gruppen omfattende akrylonitril, N-(alkyl)akrylamid, med fra 1-3 karbonatomer i alkylgruppene, metakrylamid, N-(alkyl)metakrylamid med fira 1-3 karbon--atomer i alkylgruppene, N-metylolakrylamid, N/2-(2-metyl-<1>+-oksopentyl)7akrylamid, akrylsyre, metakrylsyre og alkalimetall-og ammoniumsalter av akryl- og metakrylsyre, malein- og fumarsyre, itakon- og sitrakonsyre, halve alkylestre av malein-, fumar-, itakon- og sitrakonsyre med fra 1-6 karbonatomer i alkylgruppene, akrylyl-og. metakrylylestre av hydroksyalkansyrer med fra 2-6 karbonatomer i alkansyrene, akrylylamid og metakrylylamider av aminoalkansyrer med fra 2-6 karbonatomer i aminoalkansyren, hydroksyetyl- og hydroksypropylestre av akryl-, metakryl-, malein- og fumarsyre, vinylestre av alkansyrer med fra 1.-6 karbonatomer.og alkylsulfonsyre med fra 1-6 karbonatomer, fenylsulfonsyrer, og akrylyl- og metakrylylestre av hydroksyalkylsulfonsyre med fra 1-6 karbonatomer i alkylrestene, og hydroksyalkylsulfonamider med fra 1-6 karbonatomer i hydroksyalkylrestene,- og (b) interpolymere av den type som er beskrevet under (a) behandlet med en syre eller en base som har en ioniseringskonstant hoyere enn ca. 10 i mengder ekvivalente opp til 100. % av amidinnholdet i interpolymeren. The method according to the present invention is characterized in that the paper is coated with a mixed latex of polyvinylidene chloride polymer and interpolymer, followed by drying to remove the water, then the polymers are fused by heat into a continuous film, the interpolymer being from the group consisting of (a) an interpolymer containing from 5 - 70% ethylene, from 30 - 95% vinyl chloride and from 0.1 - 10% of at least one other polar monomer comprising at least 0.1 - 10% acrylamide, and the rest of the polar monomer content is from the group comprising acrylonitrile, N- (alkyl)acrylamide, with from 1-3 carbon atoms in the alkyl groups, methacrylamide, N-(alkyl)methacrylamide with four 1-3 carbon atoms in the alkyl groups, N-methylolacrylamide, N/2-(2-methyl-<1> +-oxopentyl)7acrylamide, acrylic acid, methacrylic acid and alkali metal and ammonium salts of acrylic and methacrylic acid, maleic and fumaric acid, itaconic and citraconic acid, half alkyl esters of maleic, fumaric, itaconic and citraconic acid with from 1-6 carbon atoms in the alkyl groups, acrylyl- and. methacrylyl esters of hydroxyalkanoic acids with from 2-6 carbon atoms in the alkanoic acids, acrylylamide and methacrylylamides of aminoalkanoic acids with from 2-6 carbon atoms in the aminoalkanoic acid, hydroxyethyl and hydroxypropyl esters of acrylic, methacrylic, maleic and fumaric acid, vinyl esters of alkanoic acids with from 1.- 6 carbon atoms and alkylsulfonic acid with from 1-6 carbon atoms, phenylsulfonic acids, and acrylyl and methacrylyl esters of hydroxyalkylsulfonic acid with from 1-6 carbon atoms in the alkyl residues, and hydroxyalkylsulfonamides with from 1-6 carbon atoms in the hydroxyalkyl residues, - and (b) interpolymers of the type which is described under (a) treated with an acid or a base which has an ionization constant higher than approx. 10 in amounts equivalent to up to 100% of the amide content in the interpolymer.
En del av akrylamidet i interpolymeren kan erstattes av polare monomere, slik som akrylonitril, N-(lavere alkyl)akrylamid.og N-(lavere alkylmetakrylamid med fra 1 til 3 karbonatomer i de lavere alkylgrupper,, N-metylolakrylamid, N/~2-(2-metyl-^--okso-pentyl)7akrylamid, akrylsyre, metakrylsyre og alkalimetall-og ammoniumsalter av akryl- og metakrylsyre, maleinsyre, fumarsyre, halve og fullstendige alkalimetall- og ammoniumsalter av malein- og fumarsyre, akonitinsyre, itakonsyre, sitrakonsyre og alkalimetall- og ammoniumsalter av disse, akrylyl- og metakrylylestre av hydroksyalkansyrer med fra 2 til 6 karbonatomer i i alkansyreandelene, akrylylamider og metakrylylamider av aminoalkanoinsyrer med fra.2 til 6 karbonatomer i aminoalkanoin-syren, hydroksyetyl- og hydroksypropylestre av akryl-, metakryl-, malein- og fumarsyre, vinylestre av alkanoinsyrer med fra 1 til 6 karbonatomer, slik som vinylacetat, vinylpropionat og lavere alkyl (1 til 6 karbonatomer) sulfonsyre, fenylsulfonsyrer og al-kylfenylsulfonsyrer og akrylyl- og metakrylylestre av hydroksy-alkylsulf onsyrer med fra 1 til 6 karbonatomer i alkylandelene, og hydroksyalkylsulfonamider med fra l.til 6 karbonatomer i hy-droksyalkylandelene. Akrylamidet skal generelt utgjore minst JO vektsk av den tredje eller polare monomer i interpolymeren, og Part of the acrylamide in the interpolymer can be replaced by polar monomers, such as acrylonitrile, N-(lower alkyl)acrylamide, and N-(lower alkyl methacrylamide with from 1 to 3 carbon atoms in the lower alkyl groups, N-methylolacrylamide, N/~2 -(2-methyl-^--oxo-pentyl)7acrylamide, acrylic acid, methacrylic acid and alkali metal and ammonium salts of acrylic and methacrylic acid, maleic acid, fumaric acid, half and complete alkali metal and ammonium salts of maleic and fumaric acid, aconitic acid, itaconic acid, citraconic acid and alkali metal and ammonium salts thereof, acrylyl and methacrylyl esters of hydroxyalkanoic acids with from 2 to 6 carbon atoms in the alkanoic acid portions, acrylyl amides and methacrylyl amides of aminoalkanoic acids with from 2 to 6 carbon atoms in the aminoalkanoic acid, hydroxyethyl and hydroxypropyl esters of acrylic, methacryl -, maleic and fumaric acid, vinyl esters of alkanoic acids with from 1 to 6 carbon atoms, such as vinyl acetate, vinyl propionate and lower alkyl (1 to 6 carbon atoms) sulfonic acid, phenylsulfonic acids and al -alkylphenylsulfonic acids and acrylyl and methacrylyl esters of hydroxyalkylsulfonic acids with from 1 to 6 carbon atoms in the alkyl parts, and hydroxyalkylsulfonamides with from 1 to 6 carbon atoms in the hydroxyalkyl parts. The acrylamide should generally make up at least JO by weight of the third or polar monomer in the interpolymer, and
fortrinnsvis danne minst 80 % av denne polare monomer. preferably form at least 80% of this polar monomer.
Således er.interpolymerene som fremstilles i vandig dispergert form i det minste terpolymere som inneholder etylen,' vinylklorid og akrylamid, og kan være en kvaternær eller hoyere polymer som inneholder en eller flere av foran som eksempler angitte ytterligere polare monomere i små mengder, men vanligvis vil slike ytterligere monomere ikke være tilstede i interpolymeren i mengder storre enn 2 vekts$. Thus, the interpolymers produced in aqueous dispersed form are at least terpolymers containing ethylene, vinyl chloride and acrylamide, and may be a quaternary or higher polymer containing one or more of the additional polar monomers exemplified above in small amounts, but usually such additional monomers will not be present in the interpolymer in amounts greater than 2% by weight.
Det er foretrukket at interpolymeren inneholder fra- 5 til 70 % etylen, 30$ til 95 % vinylklorid og fva. 1% til % akrylamid. Et spesielt valgt eksempel, som det vil forstås, er en terpolymer som inneholder fra 18 til 23$ etylen, 72 til 78$ vinylklorid og fra 2 til h% akrylamid. It is preferred that the interpolymer contains from 5 to 70% ethylene, 30% to 95% vinyl chloride and vva. 1% to % acrylamide. A particularly selected example, as will be appreciated, is a terpolymer containing from 18 to 23% ethylene, 72 to 78% vinyl chloride and from 2 to 10% acrylamide.
Skjont interpolymerene som anvendes ved utforelsen av nærværende oppfinnelse vanligvis er ikke-modifisert, omfattes også mo-difiserte interpolymere av nærværende oppfinnelse. Interpolymerene' er særlig mottagelige for hydrolytiske modifikasjoner ved anvendelse av små mengder av et sterkt alkalisk materiale, slik som et alkalimetallhydroksyd, eller et kvaternært ammoniumhy-droksyd, slik som tetrametylammoniumhydroksyd, eller av en sterk syre slik sommineralsyrene, f.eks. saltsyre, svovelsyre, fos-forsyre, salpetersyre. Basen eller syren som anvendes har-fortrinnsvis en ioniseringskonstant hoyere enn 10<_1+> ved 25°C. Although the interpolymers used in the implementation of the present invention are usually unmodified, modified interpolymers are also covered by the present invention. The interpolymers' are particularly susceptible to hydrolytic modifications using small amounts of a strong alkaline material, such as an alkali metal hydroxide, or a quaternary ammonium hydroxide, such as tetramethylammonium hydroxide, or of a strong acid such as the mineral acids, e.g. hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid. The base or acid used preferably has an ionization constant higher than 10<_1+> at 25°C.
Hydrolysebehandlingen, som utfores med en syre eller en'base, behover "ikke å utfores i samme grad, spesielt hvis-interpolymeren inneholder polare monomere i tillegg til akrylamidet. Den vandige dispersjon eller polymere lateks av etylen, vinylklorid og akrylamid behandles vanligvis med vandig base eller syre i en mengde som er kjemisk ekvivalent opp'til ca. 100$ av amid-ekvivalenten i interpolymeren. The hydrolysis treatment, which is carried out with an acid or a base, need not be carried out to the same extent, especially if the interpolymer contains polar monomers in addition to the acrylamide. The aqueous dispersion or polymeric latex of ethylene, vinyl chloride and acrylamide is usually treated with an aqueous base or acid in an amount chemically equivalent up to about 100% of the amide equivalent in the interpolymer.
Spesielle eksempler på polare monomere" som kan brukes, som beskrevet foran, for å erstatte en del av akrylamidet i polymerene etter nærværende oppfinnelse omfatter akrylonitril, N-metyl-akrylamid, N-etylakrylamid, N-propylakrylamid, metakrylamid, akrylsyre, metakrylsyre, maleinsyre, fumarsyre, itakonsyre, akonitinsyre og sitrakonsyre og alkalimetall- og .ammoniumsalter av slike syrer, fortrinnsvis natrium-, kalium- eller ammoniumsal-tene, alkylestre av slike syrer,, f.eks. metylakrylat, etylakry-lat, butylakrylat, metylmetakrylat, butylmetakrylat, etylmeta-krylat, monoetylmaleat, dipropylfumarat, akrylyl 3-hydroksypro-pionat, metakrylyl-M—hydroksybutanoat, N-akrylylacetamid, N-meta-krylylheksamid, 2-hydroksyetyl- og 2-hydroksypropylestre av akryl-, metakryl-, malein-, fumar-, itakon-, akonitin- og sitrakonsyre, vinylformat, vinylacetat, vinylheksanoat, vinyl- og alkylestre av propansulfonsyre, vinylfenylsulfonat, akrylyl- og metakrylylestre av 2-hydroksypropylsulfonsyre og N-akrylyl- og. N-metakrylyl 2-hydroksypropanamider. Specific examples of polar monomers" which can be used, as described above, to replace part of the acrylamide in the polymers of the present invention include acrylonitrile, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, methacrylamide, acrylic acid, methacrylic acid, maleic acid , fumaric acid, itaconic acid, aconitic acid and citraconic acid and alkali metal and ammonium salts of such acids, preferably the sodium, potassium or ammonium salts, alkyl esters of such acids, e.g. methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate , ethyl methacrylate, monoethyl maleate, dipropyl fumarate, acrylyl 3-hydroxypropionate, methacrylyl M-hydroxybutanoate, N-acrylyl acetamide, N-methacrylylhexamide, 2-hydroxyethyl and 2-hydroxypropyl esters of acrylic, methacrylic, maleic, fumaric, itaconic, aconitic and citraconic acids, vinyl formate, vinyl acetate, vinyl hexanoate, vinyl and alkyl esters of propanesulfonic acid, vinylphenylsulfonate, acrylyl and methacrylyl esters of 2-hydroxypropylsulfonic acid and N-acrylyl- and. N-methacrylyl 2-hydroxypropanamides.
Etylen-j vinylklorid-; akrylamid-interpolymerene kan fremstilles ved forst å blande etyle'n og vinylklorid i et vandig medium i nærvær av et egnet anionisk eller ikke-ionisk emulgeringsmiddel i en initiator med evne til å generere frie radikaler i den kjemiske blanding ved den valgte reaksjonstemperatur og trykk. Akrylamidet, fortrinnsvis i vandig opplosning enten alene eller blandet med de egnete mengder av andre polare monomere, tilsettes til den polymeriserende etylen- og vinylkloridblanding grad-vis under reaksjonen. Da akrylamidet er meget reaksjonsvillig kan ikke alt .tilsettes ved begynnelsen av reaksjonen. Det er foretrukket å forsinke tilsetningen av akrylamidet inntil ca. Ethylene-j vinyl chloride-; The acrylamide interpolymers can be prepared by first mixing ethylene and vinyl chloride in an aqueous medium in the presence of a suitable anionic or non-ionic emulsifier in an initiator capable of generating free radicals in the chemical mixture at the selected reaction temperature and pressure. The acrylamide, preferably in aqueous solution either alone or mixed with the appropriate amounts of other polar monomers, is added to the polymerizing ethylene and vinyl chloride mixture gradually during the reaction. As the acrylamide is very reactive, not everything can be added at the beginning of the reaction. It is preferred to delay the addition of the acrylamide until approx.
^0 til 50 % av den onskete omdannelse av etylen og vinylklorid er blitt-nådd, da, ved den endelige påforing av lateksen, over-flaten av polymerpartiklene danner stedet for vedheftning. Dette gir en latekskjerne med skall, hvor den polare akrylamid er kon-sentrert i de ytre lag. 0 to 50% of the desired conversion of ethylene and vinyl chloride has been achieved when, at the final application of the latex, the surface of the polymer particles forms the site of attachment. This gives a latex core with a shell, where the polar acrylamide is concentrated in the outer layers.
Foranstående etylen/vinylklorid/akrylamid-interpolymere fremstilles lett ved forskjellige måter som er kjent på området. Etylen/vinylklorid/akrylamid-interpolymerene som anvendes ved nærværende oppfinnelse fremstilles fortrinnsvis ved en fremgangsmåte som består i å blande etylen og vinylkloridmonomere i nærvær av et alkalisk pufret redox-initiator-katalysatorsy-stem, vann og fra ca. 1% til ca. 8 vekts$ basert på innmatet monomer, eller fra ca. h til ca. 7 % basert på det polymere produkt av et anionisk eller ikke-ionisk emulgeringsmiddel som har en hydrofil-lipofil balanse- (HLB)verdi på fra 10 til ^0, og omsette blandingen ved en temperatur og .et trykk og over en tidsperiode tilstrekkelig til å forårsake polymerisasjon mellom etylen og vinylklorid, og derpå innfore akrylamid, enten alene åler blandet med andre monomere i mindre mengder i et egnet fortynningsmiddel, slik som vann, i den under trykk polymeriserende reaksjonsblanding av etylen og vinylklorid. The above ethylene/vinyl chloride/acrylamide interpolymers are readily prepared by various methods known in the art. The ethylene/vinyl chloride/acrylamide interpolymers used in the present invention are preferably prepared by a method which consists in mixing ethylene and vinyl chloride monomers in the presence of an alkaline buffered redox initiator-catalyst system, water and from approx. 1% to approx. 8 wt$ based on the monomer fed in, or from approx. h to approx. 7% based on the polymeric product of an anionic or nonionic emulsifier having a hydrophilic-lipophilic balance (HLB) value of from 10 to ^0, and reacting the mixture at a temperature and pressure and over a period of time sufficient to to cause polymerization between ethylene and vinyl chloride, and then introduce acrylamide, either alone or mixed with other monomers in smaller amounts in a suitable diluent, such as water, into the pressurized polymerizing reaction mixture of ethylene and vinyl chloride.
Fra fransk patent nr. IA78.219 er kjent forskjellige bærere som er gjort vannsikre med et overtrekk på basis av to eller flere vinylidenklorid-kopolymerer som har forskjellig natur og sammensetning og ved overtrekning med vandige emulsjoner. Disse overtrekk består av: - "fleksible" kopolymerer som inneholder vinylidenklorid og vinylklorid i et vektsforhold mellom 0,6 og ^-,0 og 1 - 100 g/ kg av en eller flere plastiserende monomerer fra gruppen umettede mono- eller polykarboksylsyreestré av mettede alkoholer med h - 18 karbonatomer, vinylestre av mettede karbok-sylsyrer med 6 - 18 karbonatomer og blandinger av disse From French patent no. IA78,219, various carriers are known which are rendered waterproof with a coating based on two or more vinylidene chloride copolymers of different nature and composition and by coating with aqueous emulsions. These coatings consist of: - "flexible" copolymers containing vinylidene chloride and vinyl chloride in a weight ratio between 0.6 and ^-.0 and 1 - 100 g/kg of one or more plasticizing monomers from the group of unsaturated mono- or polycarboxylic acid esters of saturated alcohols with h - 18 carbon atoms, vinyl esters of saturated carboxylic acids with 6 - 18 carbon atoms and mixtures thereof
estre, og esters, and
- "hårde" kopolymerer hvor vektsforholdet mellom vinylidenklorid og de andre monomerer er mellom h og ^-9, og de ovrige monomerer er fra gruppen akrylonitril, metakrylonitril, estre fra umettede mono- eller polykarboksylsyrer og mettede alkoholer med opp til h karbonatomer. - "hard" copolymers where the weight ratio between vinylidene chloride and the other monomers is between h and ^-9, and the other monomers are from the group of acrylonitrile, methacrylonitrile, esters from unsaturated mono- or polycarboxylic acids and saturated alcohols with up to h carbon atoms.
Til forskjell fra nærværende oppfinnelse er overtrekketifolge det franske patent fremstilt av to kopolymerer, i hvilke basis-bestanddelene er vinylklorid og vinylidenklorid i forskjellige basisforhold. In contrast to the present invention, according to the French patent, the coating is made from two copolymers, in which the base components are vinyl chloride and vinylidene chloride in different base ratios.
I det amerikanske patent nr. 2.91<1>+.<1>+98 er der beskrevet en blanding av polyvinylklorid eller vinylklorid-vinylidenklorid-kopolymer og poly-(N,N-dialkylakrylamid) og ikke en blanding av polyvinylidenklorid med en terpolymer laget av spesifikke mengder av etylen, vinylklorid og akrylamid med eventuelt en polar monomer slik som N-(alkyl)akrylamid. Dette patent avviker også vesentlig fra hva det åpenbares ved nærværende oppfinnelse. In US Patent No. 2.91<1>+.<1>+98 there is described a mixture of polyvinyl chloride or vinyl chloride-vinylidene chloride copolymer and poly-(N,N-dialkylacrylamide) and not a mixture of polyvinylidene chloride with a terpolymer made of specific amounts of ethylene, vinyl chloride and acrylamide with optionally a polar monomer such as N-(alkyl)acrylamide. This patent also deviates significantly from what is revealed by the present invention.
I det amerikanske patent nr. 3-<1>+28.582 beskrives Interpolymer-latekser som er anvendelige som pigmentbindemidler eller klebemidler i pigmentovertrekksblandinger for papir og er fra gruppen interpolymer som inneholder 15 - 70 % etylen, 30 - 85 % vinylklorid og 0,1 - 10 % av minst en annen polar monomer som inkluderer minst 0,1 - 10 % akrylamid og slike interpolymerer behandlet med en syre eller en base. US Patent No. 3-<1>+28,582 describes Interpolymer latexes which are useful as pigment binders or adhesives in pigment coating compositions for paper and are from the group of interpolymers containing 15 - 70% ethylene, 30 - 85% vinyl chloride and 0.1 - 10% of at least one other polar monomer which includes at least 0.1 - 10% acrylamide and such interpolymers treated with an acid or a base.
Dette patent beskjeftiger seg som det fremgår med pigmentbindemidler og klebemidler i pigmentovertrekksblandinger og vedrorer ikke et filmovertrekk for papir. Problemene som er forbundet med å meddele motstand mot olje, fett, opplosningsmidler og fuktighet foreligger ikke i dette tilfelle. As it appears, this patent deals with pigment binders and adhesives in pigment coating mixtures and does not relate to a film coating for paper. The problems associated with reporting resistance to oil, grease, solvents and moisture do not exist in this case.
De folgende detaljerte eksempler viser fremstillingen av polymere latekser som anvendes ved oppfinnelsen.' I polymer-lateks-eksemplene utfores hele polymerisasjorien i et 3820 ml's trykk-kar ved 30°C med en hastighet på 600 omdreininger pr. minutt for den roterende omrorer. The following detailed examples show the production of polymeric latexes used in the invention. In the polymer-latex examples, the entire polymerization is carried out in a 3820 ml pressure vessel at 30°C with a speed of 600 revolutions per minute. minute for the rotary agitator.
Eksempel 1. Example 1.
Dette eksempel illustrerer fremstillingen av en 21/76/3 etylen/- vinylklorid/akrylamid-terpolymerlateks, og efter-stabilisering av slik lateks med et emulgeringsmiddel. This example illustrates the preparation of a 21/76/3 ethylene/vinyl chloride/acrylamide terpolymer latex, and post-stabilization of such latex with an emulsifier.
Den forannevnte komponentblanding ble oppvarmet til 30 C under omroring for a gi et reaksjonstrykk på 59,5 kg/cm 2 manometer-trykk. Polymerisasjonen ble innledet ved å tilsette 1 M natri-umformaldehydsulfoxylat-NaHS02.CH20.2H2(SFS)/1,5 M ammoniumhy-droxyd (NH^OH) opplosning til blandingen med en hastighet på The aforementioned component mixture was heated to 30°C with stirring to give a reaction pressure of 59.5 kg/cm 2 gauge pressure. The polymerization was initiated by adding 1 M sodium formaldehyde sulfoxylate-NaHSO 2 .CH 2 O .2H 2 (SFS)/1.5 M ammonium hydroxide (NH 2 OH) solution to the mixture at a rate of
5,2 ml/time og samtidig ble 18 ml/time av en 25%'s SLS opplosning tilsatt, og trykket ble holdt konstant ved tilsetningen av rent vinylklorid efter behov. Efter at tre timer hadde forlopet, ble en 50%'s opplosning av akrylamid i vanndig opplosning tilsatt med 40 ml/time. Reaksjonen stoppet efter 5,5 timer og inn-matningsstrommene ble koblet ut. Et total på 1330 g VC1, 95 ml av det 50%'s akrylamid, 27 ml IM SFS/1,5 M NH^OH opplosning og 92 ml av den 25%'s SLS opplosning var blitt tilsatt. Den resulterende polymere lateks ble luftet av fra bunnen av autoklaven. Et total på ca. 3500 g av etylen/vinylklorid/akrylamid-polymer-lateksen ble oppnådd, som inneholder 47% faste stoffer ialt, og 1,5% natriumlaurylsulfat (basert på vekten av polymeren). Den 5.2 ml/hour and at the same time 18 ml/hour of a 25% SLS solution was added, and the pressure was kept constant by the addition of pure vinyl chloride as needed. After three hours had elapsed, a 50% solution of acrylamide in aqueous solution was added at 40 ml/hour. The reaction stopped after 5.5 hours and the feed streams were switched off. A total of 1330 g of VC1, 95 ml of the 50% acrylamide, 27 ml of IM SFS/1.5 M NH 3 OH solution and 92 ml of the 25% SLS solution had been added. The resulting polymeric latex was aerated from the bottom of the autoclave. A total of approx. 3500 g of the ethylene/vinyl chloride/acrylamide polymer latex was obtained, containing 47% total solids, and 1.5% sodium lauryl sulfate (based on the weight of the polymer). It
hadde en pH på 7,7. Sammensetningen av terpolymeren var ca. 21/ 76/3 etylen/vinylklorid/akrylamid. Efter tilsetning av 1,5% na-triumdodecylbenzensulf onat eller 3% tridecyloxy(CP^CJ^O) , var lateksen ferdig for direkte bruk som sperreovertrekk. had a pH of 7.7. The composition of the terpolymer was approx. 21/ 76/3 ethylene/vinyl chloride/acrylamide. After addition of 1.5% sodium dodecylbenzene sulfonate or 3% tridecyloxy(CP^CJ^O), the latex was ready for direct use as a barrier coating.
Eksempel 2. Example 2.
Dette eksempel illustrerer fremstillingen av den base-modifiser-te etylen/vinylklorid/akrylamid-terpolymer. This example illustrates the preparation of the base-modified ethylene/vinyl chloride/acrylamide terpolymer.
Ved bruk av samme reaksjonskar og komponenter som angitt i eksempel 1, bortsett fra at bare 10,0 g KPS og bare 0,5 g SLS ble anvendt i den opprinnelige komponentsats. SFS/NH^OH oppløsnin-gen ble tilsatt med en hastighet på 4 ml/time, og SLS oppløs-ningen ble tilsatt med 8 ml/time. Polymerisasjonsreaksjonen stoppet efter 5,75 timer med et total på ca. 1340 g vinylklorid. 100 ml akrylamidopplosning, 23 ml SFS/NS^OH opplosning og 43 ml 25%'s SLS er tilsatt. Den resulterende terpolymerlateks ble efter-stabilisert ved å blande den med ytterligere 17 ml 25%'s natriumlaurylsulfat (SLS). Den stabiliserte lateks ble derpå av-luftet fra bunnen av reaksjonskaret. Det ble oppnådd 3460 g av et materiale som inneholder totalt 49% faste stoffer, 1% SLS Using the same reaction vessel and components as stated in Example 1, except that only 10.0 g of KPS and only 0.5 g of SLS were used in the original batch of components. The SFS/NH 2 OH solution was added at a rate of 4 ml/hour, and the SLS solution was added at 8 ml/hour. The polymerization reaction stopped after 5.75 hours with a total of approx. 1340 g of vinyl chloride. 100 ml of acrylamide solution, 23 ml of SFS/NS^OH solution and 43 ml of 25% SLS are added. The resulting terpolymer latex was post-stabilized by mixing it with an additional 17 ml of 25% sodium lauryl sulfate (SLS). The stabilized latex was then deaerated from the bottom of the reaction vessel. 3460 g of a material containing a total of 49% solids, 1% SLS was obtained
og i det vesentlige den samme terpolymer som beskrevet i eksempel 1. Partikkelstorrelsen for denne polymerlateks var noe storre enn den i eksempel 1. and essentially the same terpolymer as described in example 1. The particle size for this polymer latex was somewhat larger than that in example 1.
Denne stabiliserte etylen/vinylklorid/akrylamid-terpolymerlateks ble varmet ved 50°C i 4 til 16 timer efter tilsetning av 0,4-2,0 g natriumhydroxyd (tilsatt som en 10%'s vanndig NaOH opplosning) pr. kg lateks. This stabilized ethylene/vinyl chloride/acrylamide terpolymer latex was heated at 50°C for 4 to 16 hours after addition of 0.4-2.0 g of sodium hydroxide (added as a 10% aqueous NaOH solution) per kg of latex.
Eksempel 3. Example 3.
En polymerlateks med fire monomere ble fremstilt som folger: A polymer latex with four monomers was prepared as follows:
Et reaksjonstrykkar ble opprinnelig satset med A reaction pressure vessel was originally included
9,0 g KPS 9.0 g KPS
12,0 g Na-HC0312.0 g of Na-HCO 3
0,8 g Fe(N03) 3^0 0.8 g of Fe(N03)3^O
1,5 g Na.EDTA 1.5 g Na.EDTA
' 4 ' 4
0,5 g SLS 0.5 g SLS
H20 add 1700 ml H20 add 1700 ml
575 g E 575 g E
470 g VC1 470 g VC1
Denne blanding ble forseglet og varmet til 108,5 kg/cm o. Polymerisasjonen ble innledet ved å pumpe inn i karinnholdene en 1 This mixture was sealed and heated to 108.5 kg/cm o. The polymerization was initiated by pumping into the vessel contents a 1
M SLS/1,5 M NH^OH opplosning med en hastighet på 4 ml/time. Samtidig ble en 25%'s SLS opplosning tilsatt med 10 ml/time. Vinylklorid tilstrekkelig til å holde trykket konstant ble tilsatt under reaksjonen. Efter utlopet av 3 timers polymerisasjon ble en vanndig opplosning som inneholder 40% akrylamid og 10% natriumakrylat tilsatt til reaktoren med en hastighet på 24 ml/time. Efter 6 timer stoppet reaksjonen og et total på 591 g vinylklorid, 52 ml 25%'s SLS, 27 ml SFS/NH40H og 72 ml av akrylamidopplosning/akrylatopplosning var blitt tilsatt. Uomsatt etylen og vinylklorid ble luftet av fra toppen av reaktoren for å o senke trykket til ca. 17,5 kg/cm 2, og derpå ble lateksen tatt ut fra bunnen av reaktoren. Det ble således oppnådd ca. 3060 g lateks som inneholder 43% faste stoffer og 1,1% natriumlaurylsulfat. Polymersammensetningen var en 21/76/2,3/0,7 etylen/vinylklorid/akrylamid/natriumakrylat-polymer. Den var egnet for direkte bruk som overtrekksblanding for papir og kartong. Pro-sessen ble gjentatt, idet natriumakrylatet ble erstattet med en ekvivalent mengde natriummetakrylat. Et etylen/vinylklorid/ akrylamid/natriumetakrylat med i det vesentlige samme mengder monomer oppnåes. M SLS/1.5 M NH^OH solution at a rate of 4 ml/hour. At the same time, a 25% SLS solution was added at 10 ml/hour. Vinyl chloride sufficient to keep the pressure constant was added during the reaction. After the completion of 3 hours of polymerization, an aqueous solution containing 40% acrylamide and 10% sodium acrylate was added to the reactor at a rate of 24 ml/hour. After 6 hours the reaction stopped and a total of 591 g of vinyl chloride, 52 ml of 25% SLS, 27 ml of SFS/NH 4 OH and 72 ml of acrylamide solution/acrylate solution had been added. Unreacted ethylene and vinyl chloride were vented from the top of the reactor to lower the pressure to approx. 17.5 kg/cm 2 , and then the latex was taken out from the bottom of the reactor. It was thus achieved approx. 3060 g of latex containing 43% solids and 1.1% sodium lauryl sulfate. The polymer composition was a 21/76/2.3/0.7 ethylene/vinyl chloride/acrylamide/sodium acrylate polymer. It was suitable for direct use as a coating compound for paper and board. The process was repeated, replacing the sodium acrylate with an equivalent amount of sodium methacrylate. An ethylene/vinyl chloride/acrylamide/sodium ethacrylate with essentially the same amount of monomer is obtained.
Interpolymere som fremstilles på en måte analog med metoden beskrevet i eksempel 1 er vist i tabell I. Interpolymers which are prepared in a manner analogous to the method described in Example 1 are shown in Table I.
Interpolymerene fremstilt i eksemplene 4 til 8 modifiseres med natriumhydroxyd.for å oppnå hydrolyserte polymerlatekser med folgende innhold av faste stoffer: The interpolymers prepared in examples 4 to 8 are modified with sodium hydroxide to obtain hydrolyzed polymer latexes with the following content of solids:
Eksemplene 12 - 17. Examples 12 - 17.
Ved å folge fremgangsmåten i eksempel 3 erstattes natriumakrylatet med en ekvivalent mengde av komponenten som er angitt nedenfor for å oppnå en latekspolymer som beskrevet nedenfor sammensatt av i det vesentlige samme mengder som produktet i eksempel 3. By following the procedure of Example 3, the sodium acrylate is replaced by an equivalent amount of the component indicated below to obtain a latex polymer as described below composed of substantially the same amounts as the product of Example 3.
12. Polymerkom- Hydroxyetylakrylat 12. Polymer com- Hydroxyethyl acrylate
ponenten er: Etylen/vinylklorid/akrylamid-hydroxyetylakry lat the component is: Ethylene/vinyl chloride/acrylamide-hydroxyethyl acrylate
13. Polymerkom- N-isopropylakrylamid 13. Polymer com- N-isopropylacrylamide
ponenten er: Etylen/vinylklorid/akrylamid/ ponent is: Ethylene/vinyl chloride/acrylamide/
N-isopropylakrylamid N-isopropylacrylamide
14. Polymerkom- N-etylmetakrylamid 14. Polymer com- N-ethyl methacrylamide
ponenten er: Etylen/vinylklorid/akrylamid/ ponent is: Ethylene/vinyl chloride/acrylamide/
N-etylmetakrylamid N-ethyl methacrylamide
15. Polymerkom- Et diammoniumsalt av itakonsyre ponenten er: Etylen/vinylklorid/akrylamid/ 15. Polymer component A diammonium salt of itaconic acid the component is: Ethylene/vinyl chloride/acrylamide/
diammoniumitakonat diammonium itaconate
16. Polymerkom- Monobutylsyrernaleat 16. Polymer com- Monobutyl acid rnaleate
ponenten er: Etylen/vinylklorid/akrylamid/ ponent is: Ethylene/vinyl chloride/acrylamide/
monobutylsyremaleat monobutyl acid maleate
17. Polymerkom- N-metakrylylpropionamid 17. Polymer com- N-methacrylylpropionamide
ponenten er: Etylen/vinylklorid/akrylamid/ ponent is: Ethylene/vinyl chloride/acrylamide/
N-metakrylylpr opi onamid N-methacrylyl pr opi onamide
Polyvinylidenkloridlateks og etylen/vinylklorid/akrylamid-inter-polymerlateksblandinger anvendes i slike mengder at på basis av faste stoffer utgjor etylen, vinylklorid, akrylamid interpolymerene 5% - 95% og fortrinnsvis 10% til 40% av det endelige overtrekk med polyvinylidenkloridpolymeren som utgjorende resten. Som det vil fremgå for fagmannen vil de noyaktige mengder av de to polymere som brukes variere noe avhengig av polymerartene som brukes, men vanligvis vil mengdene som er angitt umiddelbart ovenfor være utmerket egnet for å oppnå de resultater som beskrives her. De blandede polymerlatekser som anvendes for å overtrekke de fibrose substrater fremstilles vanligvis ved en-kelt å blande sammen de egnede lateksarter. Vanligvis vil hver av polymerlateksene opprinnelig fremstilles ved en emulsjons-prosess. Uttrykkene "lateks" og "polymeremulsjoner" anvendes her i deres vanlige betydning, i hvilke mediet i hvilket polymerene er dispergert av vann. Polyvinylidene chloride latex and ethylene/vinyl chloride/acrylamide inter-polymer latex mixtures are used in such amounts that, on a solids basis, the ethylene, vinyl chloride, acrylamide interpolymers make up 5% - 95% and preferably 10% to 40% of the final coating with the polyvinylidene chloride polymer making up the rest. As will be apparent to those skilled in the art, the exact amounts of the two polymers used will vary somewhat depending on the polymer species used, but generally the amounts indicated immediately above will be perfectly suitable for achieving the results described herein. The mixed polymer latexes that are used to coat the fibrous substrates are usually produced by simply mixing together the suitable latex species. Usually, each of the polymer latexes will initially be produced by an emulsion process. The terms "latex" and "polymer emulsions" are used herein in their usual sense, in which the medium in which the polymers are dispersed is water.
De fibrose substrater på hvilke blandingene påfores ved utforelsen av nærværende oppfinnelse omfatter papir av alle arter slik som skrivepapir, fibros kartong, slik som vanlig kartong, eskekartong, kartong-råmateriale og liknende, innpakningspapir eller foringer for beholdere bestemt for næringsmidler, fett, tyggegummi, såpe, såpepulvre, kosmetika, kalkerende forbindel-ser, etc.. De overtrukne papirer kan også anvendes som tapeter, papir for foring av skuffer og hyller, særlig i lintoysskap, kjokkenskap og liknende, og det overtrukne papir eller kartong kan også brukes som bokbind eller boksider. The fibrous substrates on which the mixtures are applied in the embodiment of the present invention include paper of all kinds such as writing paper, fibrous cardboard, such as ordinary cardboard, box cardboard, cardboard raw material and the like, wrapping paper or linings for containers intended for foodstuffs, fats, chewing gum, soap, soap powder, cosmetics, calcareous compounds, etc. The coated papers can also be used as wallpaper, paper for lining drawers and shelves, especially in linen cupboards, kitchen cupboards and the like, and the coated paper or cardboard can also be used as book bindings or book pages.
Overtrekkene kan også påfores papir og papp, for bygningsformål slik som tapeter eller veggplater. De kan også brukes som et avrivningsovertrekk på papir som anvendes som en foring i be-tongstopeformer eller tilpasset for anvendelse for å dekke ny-lagte betongveier. The covers can also be applied to paper and cardboard, for building purposes such as wallpaper or wall panels. They can also be used as a tear-off coating on paper that is used as a lining in concrete stop molds or adapted for use to cover newly laid concrete roads.
Det fibrose substrat, f.eks. papir, som kan overtrekkes ifolge nærværende oppfinnelse med blandinger av polyvinylidenklorid-polymerlateks og etylen/vinylklorid/akrylamid-interpolymerlateks for å gi et produkt med forokete sperreegenskaper kan inneholde fra ca. 0,225 - 40,8 kg lateksblanding pr. side pr. ris. Vanligvis er imidlertid ca. 0,45 - 9 kg lateksblanding pr. ris ade-kvat, mens 0,45 kg - 1,8 kg er alt hva som er nodvendig for mange formål. The fibrous substrate, e.g. paper, which can be coated according to the present invention with mixtures of polyvinylidene chloride polymer latex and ethylene/vinyl chloride/acrylamide interpolymer latex to give a product with increased barrier properties can contain from approx. 0.225 - 40.8 kg of latex mixture per page per rice. Usually, however, approx. 0.45 - 9 kg of latex mixture per rice ade-quat, while 0.45 kg - 1.8 kg is all that is needed for many purposes.
Fremgangsmåtene for å påfore lateksovertrekket på det fibrose substrat er velkjent på området. Slike arbeidsmåter omfatter på-sproytning, valsepåforing, luftknivpåforing, påforing med beve^The methods for applying the latex coating to the fibrous substrate are well known in the art. Such working methods include spraying, roller application, air knife application, vibration application
gelige blad, filmovertrekk og bruk av en Mayer-maskin. gelled leaves, film covers and the use of a Mayer machine.
De folgende eksempler illustrerer de fordelaktige og uventede egenskaper som oppnåes ved bruk av lateksblandingene efter nærværende oppfinnelse som overtrekksmaterialer på fibrost substrat. The following examples illustrate the advantageous and unexpected properties which are obtained by using the latex mixtures according to the present invention as coating materials on fibrous substrates.
Lateksblandingen påfores filtsiden av substratet ved hjelp av The latex mixture is applied to the felt side of the substrate using
en viklet virestang. Overtrekksstang nr. 6, 18 og 28 anvendes for å påfore filmen. En nr. 6 stang har en mindre virediameter og flere viklinger for en gitt stanglengde som avsetter en tynn kontinuerlig fuktig film, mens nr. 28 stangen har storre virediameter og ferre viklinger pr. lengdeenhet og avsetter en langt tykkere■film. a coiled wire rod. Covering rod nos. 6, 18 and 28 are used to apply the film. A No. 6 rod has a smaller wire diameter and more turns for a given length of rod which deposits a thin continuous moist film, while the No. 28 rod has a larger wire diameter and four turns per unit length and deposits a much thicker■film.
Det fibrose substrat, f.eks. papir, anbringes på en plan glass-overflate, og stangen av viklet vire anbringes i nedtrekksstangen som er anbragt ved toppen av arket, og lateksblandingen helles derefter over substratbanen like overfor denne stang, nedtrekksstangen trekkes med ensartet hastighet over substratet og efterlater en ensartet, jevn lateksfilm. Alle overtrukne papirer får lufttorke over natten, utsettes derefter for 120°C i 2 minutter og kalandreres. The fibrous substrate, e.g. paper, is placed on a flat glass surface, and the rod of coiled wire is placed in the pull-down rod located at the top of the sheet, and the latex mixture is then poured over the substrate web directly opposite this rod, the pull-down rod is pulled at a uniform speed over the substrate, leaving a uniform, even latex film. All coated papers are air dried overnight, then exposed to 120°C for 2 minutes and calendered.
En rekke papirark ble overtrukket med lateksblandinger, slik A series of paper sheets were coated with latex compositions, like this
som vist i tabell II og inneholder forskjellige mengder polyvinylidenkloridpolymer og etylen, vinylklorid, akrylamid-interpolymere.. I disse eksempler er alle deler efter vekt. Overtrekkene proves derefter på forskjellige fysikalske egenskaper. Prøveme-toden beskrives i det folgende, og resultatene er angitt i tabellene III og IV. as shown in Table II and containing various amounts of polyvinylidene chloride polymer and ethylene, vinyl chloride, acrylamide interpolymers.. In these examples, all parts are by weight. The coatings are then tested for different physical properties. The test method is described below, and the results are given in Tables III and IV.
Prøvemetodene som anvendes for å bestemme de fysikalske egenskaper for de fibrose substrater som er overtrukne med lateksblandingen efter nærværende oppfinnelse angis nedenfor med for-klarende bemerkninger hvor nødvendig. Provene ble kondisjonert ifolge TAPPI. T402m-49 for undersokelse. Papirbasismaterialet som anvendes ved undersøkelsene beskrevet i det folgende er angitt hvor anvendelige for de individuelle eksempler. The test methods used to determine the physical properties of the fibrous substrates which are coated with the latex mixture according to the present invention are set out below with explanatory notes where necessary. The samples were conditioned according to TAPPI. T402m-49 for examination. The paper base material used in the investigations described in the following is indicated as applicable for the individual examples.
Qljemotstandsevne - Krollet boksprove - Et proveemne 15 x 15 cm overtrukket på en side, foldes diagonalt fra hjorne til hjorne, og hver fold utsettes for et trykk på 2,25 kg. Emnet foldes ytterligere 2,5 cm fra hver kant og boyes derefter opp til en boks med sidekanter 10 x 10 cm og sidevegger 2,5 cm med den overtrukne overflate innvendig. Alle kroller bortsett fra de som er ved sideveggene konvergerer i vinkel mot sentret av boks-bunnen. 50 cm 3 nr. 10 SAE olje helles i boksen og tiden som er nodvendig for å trenge gjennom de krollede områder noteres. Heat resistance - Rolled box test - A test piece 15 x 15 cm coated on one side, folded diagonally from corner to corner, and each fold subjected to a pressure of 2.25 kg. The blank is folded a further 2.5 cm from each edge and then bent up into a box with side edges 10 x 10 cm and side walls 2.5 cm with the coated surface inside. All curls except those at the side walls converge at an angle to the center of the box bottom. 50 cm 3 of No. 10 SAE oil is poured into the can and the time required to penetrate the curled areas is noted.
Fuktighet - Damptransmisionshastiqhet - A.S.T.M. 3-988 (tropisk atmosfære) - Angitt som gram H^O/lOO cm<2>/24 timer ved 38°C og 90%'s relativ fuktighet. Blandingene i tabell II ble anvendt for å fremstille en rekke overtrukne papirer av 30 lb blå-hvitt pergamymateriale ved å påfore to overtrekk på hver blanding på en side av hvert ark med en nr. 6 stang. Vanndamptransmisjonshastighetene for de overtrukne papirer er angitt i tabell III. Humidity - Vapor transmission speed - A.S.T.M. 3-988 (tropical atmosphere) - Expressed as grams H^O/lOO cm<2>/24 hours at 38°C and 90% relative humidity. The blends in Table II were used to prepare a series of coated papers from 30 lb. blue-white vellum material by applying two coats of each blend to one side of each sheet with a No. 6 rod. The water vapor transmission rates for the coated papers are given in Table III.
Oljemotstandsegenskapene som oppnåes med en rekke papirmateria-ler av 50 lb bleket kraft, dobbelt overtrukket med en nr. 6 stang på en side av hvert ark med blandingene i tabell II er vist i tabell IV. The oil resistance properties obtained with a variety of 50 lb. bleached kraft paper stocks, double coated with a No. 6 bar on one side of each sheet with the compositions of Table II are shown in Table IV.
Resultatene som angis i tabell III og IV viser at blandingene The results given in Tables III and IV show that the mixtures
B til P meddeler papiret den onskede kombinasjon av motstandsevne mot olje og vanndamp og god fleksibilitet. En slik kombinasjon av egenskaper er ikke oppnåelig når polyvinylidenkloridpolymer anvendes som eneste overtrékksmateriale. B to P gives the paper the desired combination of resistance to oil and water vapor and good flexibility. Such a combination of properties is not achievable when polyvinylidene chloride polymer is used as the only coating material.
Erstatning av latekser 1, 2 og 8 i blandingene B til P med eksempel 3 til 7 og 9 til 17 resulterer i overtrukne papirer som har egenskaper liknende dem som angis i tabellene III og IV. Papp, slik som kartong, kartongmateriale og eskekartong viser liknende utmerkede egenskaper som vist i tabellene III og IV, når de overtrekkes med lateksblandingene efter nærværende oppfinnelse. Substitution of latexes 1, 2 and 8 in blends B to P with examples 3 to 7 and 9 to 17 results in coated papers having properties similar to those listed in Tables III and IV. Cardboard, such as cardboard, cardboard material and boxed cardboard show similarly excellent properties as shown in Tables III and IV, when coated with the latex compositions according to the present invention.
Papiret som overtrekkes kan være av en rekke arter, inklusive finpapir, skrivepapir, pergament, etc. Arten, vekten og andre fysikalske egenskaper for papirer på hvilke overtrekket påfores innvirker ikke vesentlig på forbedringen i motstandsevnen mot ol-je og fuktig damptransmisjonshastigheten som oppnåes ved metoden ifolge oppfinnelsen. The paper that is coated can be of a variety of species, including fine paper, writing paper, parchment, etc. The nature, weight and other physical properties of papers to which the coating is applied do not significantly affect the improvement in resistance to oil and moisture vapor transmission rate achieved by the method according to the invention.
De overtrukne papirer som oppnåes ved nærværende oppfinnelse The coated papers obtained by the present invention
har anvendelighet for mange formål som vil være klare for fagmannen. Særlig kan de overtrukne papirer anvendes til innpak-ning av næringsmidler hvor det er onsket å forebygge overforin-gen av fuktighet fra atmosfæren til det pakkede produkt. De overtrukne papirer varmeforsegles lett og motstår væsker godt. Resultatet er at slike overtrukne papirer kan brukes ved fremstillingen av papirdrikkekopper og liknende. has applicability for many purposes which will be clear to those skilled in the art. In particular, the coated papers can be used for wrapping foodstuffs where it is desired to prevent the transfer of moisture from the atmosphere to the packaged product. The coated papers are easily heat-sealed and resist liquids well. The result is that such coated papers can be used in the production of paper drinking cups and the like.
Claims (5)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US71836768A | 1968-04-03 | 1968-04-03 |
Publications (1)
Publication Number | Publication Date |
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NO127413B true NO127413B (en) | 1973-06-18 |
Family
ID=24885835
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO141369A NO127413B (en) | 1968-04-03 | 1969-04-02 |
Country Status (3)
Country | Link |
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JP (1) | JPS505734B1 (en) |
FI (1) | FI56041C (en) |
NO (1) | NO127413B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50146836U (en) * | 1974-05-20 | 1975-12-05 | ||
JPS5195549U (en) * | 1975-01-27 | 1976-07-31 |
-
1969
- 1969-04-02 JP JP2488869A patent/JPS505734B1/ja active Pending
- 1969-04-02 FI FI96769A patent/FI56041C/en active
- 1969-04-02 NO NO141369A patent/NO127413B/no unknown
Also Published As
Publication number | Publication date |
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FI56041C (en) | 1979-11-12 |
FI56041B (en) | 1979-07-31 |
JPS505734B1 (en) | 1975-03-06 |
DE1917054B2 (en) | 1974-10-10 |
DE1917054A1 (en) | 1969-10-16 |
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