DE1546369C3 - Process for making paper, paperboard and the like with improved wet strength. Eliminated from: 1177824 - Google Patents
Process for making paper, paperboard and the like with improved wet strength. Eliminated from: 1177824Info
- Publication number
- DE1546369C3 DE1546369C3 DE1546369A DE1546369A DE1546369C3 DE 1546369 C3 DE1546369 C3 DE 1546369C3 DE 1546369 A DE1546369 A DE 1546369A DE 1546369 A DE1546369 A DE 1546369A DE 1546369 C3 DE1546369 C3 DE 1546369C3
- Authority
- DE
- Germany
- Prior art keywords
- resin
- water
- epichlorohydrin
- added
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000123 paper Substances 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 16
- 230000008569 process Effects 0.000 title claims description 6
- 239000011087 paperboard Substances 0.000 title description 2
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 239000000835 fiber Substances 0.000 claims description 19
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- -1 saturated aliphatic dicarboxylic acids Chemical class 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000011111 cardboard Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 11
- 239000004744 fabric Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 229920006122 polyamide resin Polymers 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229940037003 alum Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- RYOCYIVCDUMYAL-VFQQELCFSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;oxirane Chemical compound C1CO1.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO RYOCYIVCDUMYAL-VFQQELCFSA-N 0.000 description 1
- MSMZOAKJQHTHLP-UHFFFAOYSA-N (3-chlorooxy-2-hydroxypropyl) hypochlorite Chemical compound ClOCC(O)COCl MSMZOAKJQHTHLP-UHFFFAOYSA-N 0.000 description 1
- OCANCGNUSHKXGR-UHFFFAOYSA-N 2,3-dihydroxypropyl hypochlorite Chemical compound OCC(O)COCl OCANCGNUSHKXGR-UHFFFAOYSA-N 0.000 description 1
- JJLGDPNMAWKKAU-UHFFFAOYSA-N 2-methylprop-2-enamide;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(N)=O JJLGDPNMAWKKAU-UHFFFAOYSA-N 0.000 description 1
- VSGKEWJNJIONGY-UHFFFAOYSA-N 2-methylprop-2-enenitrile;prop-2-enoic acid Chemical compound CC(=C)C#N.OC(=O)C=C VSGKEWJNJIONGY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002943 palmitic acids Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
- D06M15/595—Derivatives obtained by substitution of a hydrogen atom of the carboxamide radical
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Polyamides (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Papier, Pappe u. dgl. mit verbesserter Naßfestigkeit aus Cellulosefasern durch Imprägnierung der in wäßriger Suspension gehaltenen Cellulosefasern mit einem warmhärtbaren Epichlorhydrin-Harz, Ablagerung eines Papierbogens aus der Suspension und Aushärtung des Harzes auf den Fasern.The present invention relates to a process for the production of paper, cardboard and the like with improved Wet strength from cellulose fibers by impregnation of the cellulose fibers kept in aqueous suspension with a thermosetting epichlorohydrin resin, deposition of a sheet of paper from the suspension and curing the resin on the fibers.
Aus der USA.-Patentschrift 2 595 935 ist es bekannt, die Naßfestigkeit von Papier zu verbessern durch Zusatz eines warmhärtbaren Alkylenpolyamin-Epichlorhydrin-Harzes zu der wäßrigen Suspension der Papierrohmasse. From US Pat. No. 2,595,935 it is known to improve the wet strength of paper by adding it a thermosetting alkylene polyamine-epichlorohydrin resin to the aqueous suspension of the paper pulp.
Demgegenüber betrifft die nicht vorveröffentlichte deutsche Patentschrift 1 177 824 ein Verfahren zur Herstellung von verbesserten, wasserlöslichen Kondensaten aus Polyamiden und Epichlorhydrin durch Umsetzung von Polyamiden in wäßriger Lösung mit Epichlorhydrin, das dadurch gekennzeichnet ist, daß man Polyamide, die durch Polykondensieren von gesättigten aliphatischen Dicarbonsäuren mit 3 bis 10 Kohlenstoffatomen und mehrwertigen Aminen der allgemeinen Formel NH2 — (CnH2nNH)jH, in der ηIn contrast, the unpublished German patent 1 177 824 relates to a process for the preparation of improved, water-soluble condensates from polyamides and epichlorohydrin by reacting polyamides in aqueous solution with epichlorohydrin, which is characterized in that polyamides obtained by polycondensation of saturated aliphatic dicarboxylic acids with 3 to 10 carbon atoms and polyvalent amines of the general formula NH 2 - (CnH 2 nNH) jH, in which η
ίο und .v ganze Zahlen im Wert von mindestens 2 bedeuten, in einem Molverhältnis zu den Dicarbonsäuren von 0,8 : 1 bis 1,4: 1 bei Temperaturen von 110 bis 250° C hergestellt worden sind, in an sich bekannter Weise mit Epichlorhydrin bei Temperaturen von 45 bis 1000C umsetzt. Die in dieser Weise erhaltenen kationischen Harze sind für eine Anzahl von Verwendungen brauchbar. Eine von diesen ist das Naßfestmachen von Papier, Pappe und ähnlichen faserigen Produkten aus Cellulosefasern.ίο and .v mean integers with a value of at least 2, in a molar ratio to the dicarboxylic acids of 0.8: 1 to 1.4: 1 at temperatures of 110 to 250 ° C, in a known manner with epichlorohydrin at temperatures of 45 to 100 0 C converts. The cationic resins so obtained are useful for a number of uses. One of these is the wetting of paper, paperboard and similar fibrous products made from cellulosic fibers.
Das erfindungsgemäße Verfahren zur Herstellung von Papier, Pappe u. dgl. ist somit dadurch gekennzeichnet, daß der wäßrigen Fasersuspension ein PoIyamid-Epichlorhydrin-Kondensat, das durch Polykondensieren von gesättigten aliphatischen Dicarbonsäuren mit 3 bis 10 Kohlenstoffatomen und mehrwertigen Aminen der allgemeinen FormelThe method according to the invention for the production of paper, cardboard and the like is thus characterized in that that the aqueous fiber suspension is a polyamide-epichlorohydrin condensate, by polycondensing saturated aliphatic dicarboxylic acids with 3 to 10 carbon atoms and polyvalent ones Amines of the general formula
NH2-(CnH2nNH)x)H,NH 2 - (C n H 2n NH) x ) H,
in der η und χ ganze Zahlen im Wert von mindestens 2 bedeuten, in einem Molverhältnis zu den Dicarbonsäuren von 0,8: 1 bis 1,4: 1 bei Temperaturen von 110 bis 250°C und Umsetzung der so erhaltenen Polyamide in an sich bekannter Weise mit Epichlorhydrin bei Temperaturen von 45 bis 1000C hergestellt worden ist, in einer Menge von 0,1 bis 5 Gewichtsprozent, bezogen auf das Trockengewicht der Fasern, zugesetzt wird.in which η and χ are integers with a value of at least 2, in a molar ratio to the dicarboxylic acids of 0.8: 1 to 1.4: 1 at temperatures of 110 to 250 ° C. and conversion of the polyamides obtained in this way into known per se Way with epichlorohydrin at temperatures of 45 to 100 0 C, is added in an amount of 0.1 to 5 percent by weight, based on the dry weight of the fibers.
Bei der Ausführung des Verfahrens wird eine wäßrige Lösung des Harzes in seinem ungehärteten und hydrophilen Zustand zu einer wäßrigen Suspension der Papiermasse in Holländer, Vorratskasten, Jordanmaschine, Flügelpumpe, Kopfkasten, oder an irgendeiner anderen geeigneten Stelle vor der Blattbildung zugesetzt. Das Blatt wird dann in üblicher Weise gebildet und getrocknet, wodurch das Harz zu seinem polymerisierten und wasserunlöslichen Zustand gehärtet wird.In carrying out the process, an aqueous solution of the resin in its uncured and hydrophilic state to an aqueous suspension of the paper pulp in Hollander, storage box, Jordan machine, Vane pump, head box, or any other suitable location prior to foliation added. The sheet is then formed and dried in the usual manner, thereby making the resin its own polymerized and water-insoluble state is hardened.
Die Harze können unter sauren, neutralen oder alkalischen Bedingungen gehärtet werden, das ist bei
pH-Werten von etwa 4 bis 10, indem das Papier einer Wärmebehandlung von etwa 0,5 bis 30 Minuten bei
einer Temperatur von etwa 90 bis 1000C unterworfen
wird. Beste Ergebnisse werden jedoch unter alkalischen Bedingungen erhalten. Im Hinblick hierauf
und auf die verhältnismäßig starke Korrosion der Anlage bei pH-Werten unter etwa 6,0 wird vorzugsweise
das Härten bei einem pH von etwa 6,0 bis 9,0 durchgeführt.
Vorzugsweise werden der wäßrigen Fasersuspension außerdem 0,25 bis 10 Gewichtsprozent, bezogen auf
das Trockengewicht der Fasern, eines wasserlöslichen, Carboxylgruppen enthaltenden Polymeren und/oder
0,1 bis 5 Gewichtsprozent, bezogen auf das Trocken^ gewicht der Fasern, eines wasserunlöslichen Überzugs-,
Imprägnierungs- und/oder Leimungsmittels zugesetzt. Das Epichlorhydrinharz verbessert nicht nur die
Flockung und Ablagerung der wasserlöslichen, Carboxylgruppen enthaltenden Polymeren auf den Fasern,The resins may be cured under acid, neutral or alkaline conditions, which is at a pH of about 4 to 10 by the paper is subjected to a heat treatment of about 0.5 to 30 minutes at a temperature of about 90 to 100 0 C. . However, best results are obtained under alkaline conditions. In view of this and the relatively severe corrosion of the system at pH values below about 6.0, the hardening is preferably carried out at a pH of about 6.0 to 9.0.
Preferably, 0.25 to 10 percent by weight, based on the dry weight of the fibers, of a water-soluble polymer containing carboxyl groups and / or 0.1 to 5 percent by weight, based on the dry weight of the fibers, of a water-insoluble coating, Impregnation and / or sizing agent added. The epichlorohydrin resin not only improves the flocculation and deposition of the water-soluble, carboxyl group-containing polymers on the fibers,
sondern dient auch dazu, sie auf den Fasern durch die Bildung einer direkten Bindung zwischen dem kationischen Harz und dem wasserlöslichen, Carboxylgruppen enthaltenden Polymeren und durch die Affinität des kationischen Harzes zur Faser zu verankern. Bei der Verwendung dieser Harze in Verbindung mit wasserunlöslichen Überzugs- oder Imprägnierungsmitteln wird verbessertes Festhalten solcher Mittel durch die Faser gleichfalls erreicht. Überdies haben in jedem Fall die erhaltenen Produkte verbesserte Eigenschaften, z. B. verbesserte Naß- und Trockenfestigkeit usw.but also serves to keep them on the fibers by forming a direct bond between the cationic Resin and the water-soluble, carboxyl group-containing polymer and by the To anchor the affinity of the cationic resin to the fiber. When using these resins in conjunction with water-insoluble coating or impregnating agents there is improved retention of such Means also achieved through the fiber. Moreover, in each case, the products obtained have improved Properties, e.g. B. improved wet and dry strength etc.
Das kationische Harz und das Überzugs- oder Imprägnierungsmittel werden vorzugsweise zu der wäßrigen Stoffsuspension in Form von wäßrigen Lösungen oder im Fall von wasserunlöslichen Überzugs- oder Imprägnierungsmitteln in Form einer wäßrigen Emulsion oder Dispersion zugesetzt. Die Reihenfolge des kationischen Harzes und des Überzugs- oder Imprägnierungsmittels ist zwar nicht entscheidend, aber doch wichtig für das Erreichen der besten Ergebnisse. So werden im Falle von wasserlöslichen Oberzugsoder Imprägnierungsmitteln beste Ergebnisse, z. B. größte Zunahme in der Trocken- und Naßfestigkeit erreicht, wenn das kationische Harz zur wäßrigen Stoffsuspension zuerst zugesetzt und gründlich vermischt wird vor dem Zusatz des wasserlöslichen Überzugs- und Imprägnierungsmittels. Im Falle von wasserunlöslichen Überzugs- oder Imprägnierungsmitteln hängt die Reihenfolge des Zusatzes im hohen Grade von der Menge an verwendetem kationischen Harz ab. So werden, wenn weniger als etwa 0,5 bis etwa 0,6% des kationischen Harzes angewendet wird, beste Ergebnisse erhalten, wenn das wasserunlösliche Überzugs- oder Imprägnierungsmittel zuerst zugesetzt und gründlich mit dem Stoff vermischt wird, bevor das kationische Harz zugefügt wird. Wenn mehr als 0,5 bis etwa 0,6 % Harz verwendet wird, ist es besser, das Harz zuerst zuzusetzen.The cationic resin and the coating or impregnating agent preferably become the aqueous one Stock suspension in the form of aqueous solutions or in the case of water-insoluble coating or Impregnating agents added in the form of an aqueous emulsion or dispersion. The order of the cationic resin and the coating or impregnating agent is not critical, but but important for achieving the best results. So in the case of water-soluble coverings or Impregnation agents give best results, e.g. B. largest increase in dry and wet strength achieved when the cationic resin is first added to the aqueous pulp suspension and mixed thoroughly before the addition of the water-soluble coating and impregnating agent. In case of Water-insoluble coating or impregnating agents depend on the order of addition in the high Depending on the amount of cationic resin used. So if less than about 0.5 to about 0.6% of the cationic resin is applied, best results are obtained when the water-insoluble Coating or impregnating agent is added first and mixed thoroughly with the fabric before the cationic resin is added. If more than 0.5 to about 0.6% resin is used, it is better that that Add resin first.
Eine weite Mannigfaltigkeit von wasserlöslichen oder wasserunlöslichen Überzugs- oder Imprägnierungsmitteln kann in vorteilhafter Weise unter Verwendung der Epichlorhydrin-Harze aufgebracht werden. So kann jedes wasserlösliche oder wasserdispergierbare Carboxylgruppen enthaltende Polymer in dieser Weise aufgebracht werden. Beispiele sind Polymere und Mischpolymere von Acrylsäure und Methacrylsäure, wie z. B. Acrylamid-Acrylsäure, Methacrylamid-Acrylsäure, Acrylonitril-Acrylsäure, Methacrylonitril - Acrylsäure, Mischpolymere, welche ein oder mehrere Alkylacrylate und Acrylsäure enthalten, Mischpolymere aus einem oder mehreren Alkylmethacrylaten und Acrylsäure, Mischpolymere aus einem oder mehreren Alkylvinyläthern und Acrylsäure, und gleiche Mischpolymere, in welchen Methacrylsäure an Stelle von Acrylsäure in den obigen Beispielen eingesetzt ist, wasserlösliche Celluloseäther wie Carboxymethylcellulose, Carboxymethylhydroxyäthylcellulose usw., die Alkali- und Ammoniumsalze der wasserlöslichen Celluloseäther, die Alkalisalze von Harz einschließlich Balsamharz, Harzgummen und Tallölharz, die Alkalisalze von modifiziertem Harz, wie disproportioniertem, polymerisiertem und teilweise hydriertem Harz, die Alkalisalze von Addukten von Harz mit Stoffen wie Maleinsäure, Fumarsäure, Itaconsäure oder den Anhydriden dieser Säuren, und die Alkalisalze von verschiedenen gesättigten oder ungesättigten Fettsäuren mit etwa 10 bis 22 Kohlenstoffatomen.A wide variety of water-soluble or water-insoluble coating or impregnating agents can be applied advantageously using the epichlorohydrin resins. So any water-soluble or water-dispersible carboxyl group-containing polymer in applied this way. Examples are polymers and copolymers of acrylic acid and methacrylic acid, such as B. acrylamide-acrylic acid, methacrylamide-acrylic acid, acrylonitrile-acrylic acid, methacrylonitrile - acrylic acid, mixed polymers containing one or more alkyl acrylates and acrylic acid, Mixed polymers of one or more alkyl methacrylates and acrylic acid, mixed polymers of one or more alkyl vinyl ethers and acrylic acid, and the same copolymers in which methacrylic acid is used instead of acrylic acid in the above examples, water-soluble cellulose ethers such as carboxymethyl cellulose, Carboxymethylhydroxyäthylcellulose, etc., the alkali and ammonium salts of the water-soluble Cellulose ethers, the alkali salts of resin including gum rosin, rosin gums and tall oil resin, the alkali salts of modified resin such as disproportionated, polymerized and partially hydrogenated Resin, the alkali salts of adducts of resin with substances such as maleic acid, fumaric acid, itaconic acid or the anhydrides of these acids, and the alkali salts of various saturated or unsaturated fatty acids having about 10 to 22 carbon atoms.
Beispiele von Acrylsäurepolymeren und Mischpolymeren, mit welchen die Epichlorhydrin-Harze verwendet werden können, sind solche nach der USA.-Patentschrift 2 661 309 und kanadischen Patentschrift 597 013.Examples of acrylic acid polymers and copolymers with which the epichlorohydrin resins are used are those of U.S. Patent 2,661,309 and Canadian Patent 597 013.
Die wasserlöslichen oder wasserdispergierbaren Verbindungen, mit welchen die hier beschriebenen Harze auch mit Vorteil verwendet werden können, schließen auch Kondensate niederer Alkylenoxyde mit PoIymeren von Acrylsäure, Methacrylsäure und Itaconsäure mit durchschnittlichen Molekulargewichten von etwa 1000 ein sowie Kondensate von niedrigen Alkylenoxyden mit Mischpolymeren von Acrylsäure, Methacrylsäure und Itaconsäure mit mindestens einem Gehalt von 35 Molprozent, und vorzugsweise mindestens etwa 50 Molprozent, von einer oder mehreren dieser Säuren als die einzusetzenden Monomereinheiten. Polymerisierbare Verbindungen, welche mit einer oder mehreren dieser Säuren oder mit Salzen solcher Säuren mischpolymerisiert werden können, schließen ein die Ester von Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure, Fumarsäure und Citraconsäure, und einwertige Alkohole wie Methyl-, Butyl-, Octyl-, Dodecyl-, Cyclohexylalkohol usw., Vinyl- und Vinyloxyalkylester von Carbonsäuren wie Essigsäure, Propionsäure u. dgl., Vinyläther wie Äthylvinyläther und Butylvinyläther, Acrylamide, Methacrylamide usw. Die Herstellung dieser Carboxylgruppen enthaltenden Polymeren und Mischpolymeren und ihre Kondensation mit Alkylenoxyden kann nach bekannten Verfahren ausgeführt werden. Bei der letzteren Reaktion kann das Verhältnis des eingeführten Alkylenoxyds von etwa 1 Molprozent bis 250 Molprozent, und vorzugsweise zwischen 18 und etwa 95 Molprozent, der Carboxylgruppen enthaltenden Einheiten des Polymers schwanken.The water-soluble or water-dispersible compounds with which the resins described herein Can also be used with advantage, also include condensates of lower alkylene oxides with polymers of acrylic acid, methacrylic acid and itaconic acid with average molecular weights of about 1000 a and condensates of lower alkylene oxides with copolymers of acrylic acid, Methacrylic acid and itaconic acid at a level of at least 35 mole percent, and preferably at least about 50 mole percent of one or more of these acids as the monomer units to be employed. Polymerizable compounds, which with one or more of these acids or with salts such acids can be copolymerized include the esters of acrylic acid, methacrylic acid, Itaconic acid, maleic acid, fumaric acid and citraconic acid, and monohydric alcohols such as methyl, butyl, Octyl, dodecyl, cyclohexyl alcohol, etc., vinyl and vinyloxyalkyl esters of carboxylic acids such as acetic acid, Propionic acid and the like, vinyl ethers such as ethyl vinyl ether and butyl vinyl ether, acrylamides, methacrylamides etc. The preparation of these carboxyl group-containing polymers and copolymers and their Condensation with alkylene oxides can be carried out by known methods. In the In the latter reaction, the ratio of the alkylene oxide introduced can be from about 1 mole percent to 250 mole percent, and preferably between 18 and about 95 mole percent of the carboxyl groups Units of the polymer vary.
Die wasserunlöslichen Überzugs- und Imprägnierungsmittel, welche vorteilhafterweise unter Verwendung der Epichlorhydrin-Harze aufgebracht werden können, schließen Stoffe ein wie Harze, gefällte oder unlösliche Leime, Elastomere, Wachse, Peche, Bitumina und öle, wie auch die verschiedenen Tone und/ oder Pigmente, welche bei der Herstellung von gefüllten oder/und überzogenen Papieren benutzt werden. Typische wasserunlösliche Stoffe dieser Art, welche aufgebracht werden können, sind in der USA.-Patentschrift 2 601 598 offenbart. Die Epichlorhydrin-Harze können auch in vorteilhafter Weise bei der Aufbringung von Ketendimeren auf Papier u. dgl. benutzt werden. Diese können mitunter unmittelbar in der wäßrigen Stoffsuspension dispergiert werden. Sie können auch in der Form von wäßrigen Dispersionen benutzt werden, beispielsweise wie in der USA.-Patentschrift 2 627 477 erwähnt, oder in einer beliebigen anderen geeigneten Weise, z. B. in der Form von wäßrigen Dispersionen von Ketendimerzusammenstellungen, welche auf Teilchen eines feinverteilten anorganischen Materials wie Ton, Kieselsäure u. dgl. getragenes Ketendimer enthalten. Außerdem können diese Harze in vorteilhafter Weise verwendet werden, um nichtionische und anionische Wachsemulsionen aufzutragen.The water-insoluble coating and impregnating agents which advantageously use The epichlorohydrin resins that can be applied include substances such as resins, precipitated or insoluble glues, elastomers, waxes, pitches, bitumens and oils, as well as the various clays and / or pigments, which are used in the manufacture of filled and / or coated papers. Typical water-insoluble materials of this type that can be applied are described in the United States patent No. 2,601,598. The epichlorohydrin resins can also be used in an advantageous manner during application can be used by ketene dimers on paper and the like. These can sometimes be found directly in the aqueous pulp suspension are dispersed. They can also be in the form of aqueous dispersions for example, as mentioned in U.S. Patent 2,627,477, or any in another suitable manner, e.g. B. in the form of aqueous dispersions of ketene dimer compositions, which is based on particles of a finely divided inorganic material such as clay, silica and the like. Worn ketene dimer included. In addition, these resins can be used advantageously to apply nonionic and anionic wax emulsions.
Obwohl das Epichlorhydrin-Harz vorzugsweise der Faserstoffsuspension vor der Blattbildung zugesetzt wird, kann auch vorgeformtes und teilweise oder ganz getrocknetes Papier durch Eintauchen in oder Besprühen mit einer wäßrigen Lösung des Harzes imprägniert werden, worauf das Papier für etwa 0,5 bisAlthough the epichlorohydrin resin is preferably added to the pulp suspension prior to sheet formation can also be preformed and partially or fully dried paper by dipping in or spraying be impregnated with an aqueous solution of the resin, whereupon the paper for about 0.5 to
30 Minuten auf Temperaturen zwischen 90 und 100° C oder höher zum Trocknen und Härten des Harzes in einen wasserunlöslichen Zustand erwärmt wird.30 minutes to temperatures between 90 and 100 ° C or higher to dry and harden the resin in is heated to a water-insoluble state.
Das erfindungsgemäße Verfahren ist geeignet für die Herstellung von beispielsweise Papierhandtüchern, absorbierendem Gewebe, aber auch von schwererem Material wie Einwickelpapier und Sackpapier.The method according to the invention is suitable for the production of, for example, paper towels, absorbent fabric, but also of heavier material such as wrapping paper and sack paper.
Gebleichter Kraftzellstoff wurde auf eine Schopper-Riegler-Freiheit von 750 cm3 in einem Kreislaufholländer zerkleinert. Der Stoff wurde dann auf pH 9,0 mit 10%iger NaOH eingestellt, und 1%, bezogen auf das Trockengewicht des Stoffes, an dem Polyamid-Epichlorhydrin-Harz, hergestellt nach den Beispielen 1 bis 3 der deutschen Patentschrift 1177 824, wurde zugegeben. Der Stoff wurde auf einer Handblattmaschine zu einem Blatt unter Verwendung eines geschlossenen Systems, worin das Weißwasser 100 Teile pro Million Sulfation enthielt und auf pH 9,0 mit 10%iger NaOH eingestellt war, verformt. Ein Teil der sich ergebenden Handblätter wurde während 1 Stunde bei 105° C zuzätzlich gehärtet. Die auf Naßfestigkeit geprüften Blätter wurden 2 Stunden in destilliertem Wasser eingeweicht. Die Ergebnisse folgen in Tabelle I.Bleached kraft pulp was comminuted to a Schopper-Riegler clearance of 750 cm 3 in a closed-loop dutchman. The fabric was then adjusted to pH 9.0 with 10% NaOH, and 1%, based on the dry weight of the fabric, of the polyamide-epichlorohydrin resin, prepared according to Examples 1 to 3 of German Patent 1177 824, was added . The fabric was formed into a sheet on a hand sheet machine using a closed system wherein the white water contained 100 parts per million sulfate ion and was adjusted to pH 9.0 with 10% NaOH. Some of the resulting handsheets were additionally cured for 1 hour at 105 ° C. The leaves tested for wet strength were soaked in distilled water for 2 hours. The results follow in Table I.
holländer vermählen. Das pH des Stoffs war 7,5 bis 7,8. Zu diesem Stoff wurden 1 % des nach den Beispielen 4 bis 9 der deutschen Patentschrift 1 177 824 hergestellten Polyamid-Epichlorhydrindimethylsulfatharzes, bezogen auf das Trockengewicht des Stoffes, zugesetzt. Der Stoff wurde in Blattform auf einer Handblattmaschine unter Verwendung eines geschlossenen Systems übergeführt. Das Weißwasser enthielt 200Teile pro Million Sulfation und war auf pH 7,5 eingestelltDutch wed. The pH of the fabric was 7.5 to 7.8. For this substance 1% of that according to the examples 4 to 9 of the German patent specification 1 177 824 produced polyamide-epichlorohydrin dimethyl sulfate resin, based on the dry weight of the fabric. The fabric was sheeted on a hand sheet machine transferred using a closed system. The white water contained 200 parts per million sulfate ion and was adjusted to pH 7.5
ίο worden. Die erhaltenen Handblätter wurden durch Preßwalzen geleitet und dann auf einer Trommel nach dem üblichen Verfahren getrocknet. Ein Teil der sich ergebenden Handblätter wurde während 1 Stunde bei 105° C gehärtet. Die auf Naßfestigkeit geprüften Blätter wurden 2 Stunden in destilliertem Wasser eingeweicht. Die Ergebnisse folgen in Tabelle II.ίο been. The obtained hand sheets were by Passed press rolls and then dried on a drum by the usual method. A part of resulting handsheets were cured for 1 hour at 105 ° C. Those tested for wet strength Leaves were soaked in distilled water for 2 hours. The results follow in Table II.
Beispiel der
deutschen
Patentschrift
1 177 824Resin according to
Example of
German
Patent specification
1 177 824
/o
zugesetztes
Harz, bezogen
auf Trocken-
zellstoff O/
/O
added
Resin
on dry
cellulose
gewicht
kg pro
19 350 cm2 ground
Weight
kg per
19 350 cm 2
festigkeit
kg/2,54 cmWet
strength
kg / 2.54 cm
festigkeit
gehärtet
kg/2,54 cmWet
strength
hardened
kg / 2.54 cm
2
3
ohne Zusatz1
2
3
without addition
1,0
1,0
0,01.0
1.0
1.0
0.0
17,8
18,5
18,418.4
17.8
18.5
18.4
2,7
3,4
0,092.9
2.7
3.4
0.09
3,8
3,9
0,53.8
3.8
3.9
0.5
Gebleichter Kraftzellstoff wurde auf eine Schopper-Riegler-Freiheit von 750 cm3 in einem Kreislauf-Harz gemäßBleached kraft pulp was made to a Schopper-Riegler clearance of 750 cm 3 in a cycle resin according to
deutschenGerman
PatentschriftPatent specification
1 177 8241 177 824
o/ /oO/ /O
zugesetztes Harz
Trockenstoffbasis) added resin
Dry matter basis)
Naß-Zugfestigkeit
(kg/2,54 cm Breite)Wet tensile strength
(kg / 2.54 cm width)
ungehärtet I gehärtetunhardened I hardened
4
5
6
7
8
94th
5
6th
7th
8th
9
1,01.0
1,01.0
1,0
1,0
1,0
1,01.0
1.0
1.0
1.0
2,9
2,9
2,9
2,9
2,6
2,32.9
2.9
2.9
2.9
2.6
2.3
4,0
5,0
5,2
3,9
4,1
4,24.0
5.0
5.2
3.9
4.1
4.2
') Grundgewicht aller Blätter war 18,1 ± 0,2 kg pro 19 350 cm2. Blätter aus dem gleichen StofTbrei gaben vom Filz genommen Naßzugfestigkeiten von 0,4 (ungehärtet) und 0,5 (gehärtet) kg pro 2,54 cm Breite.') Basic weight of all leaves was 18.1 ± 0.2 kg per 19,350 cm 2 . Sheets made from the same pulp gave wet tensile strengths, taken from the felt, of 0.4 (uncured) and 0.5 (cured) kg per 2.54 cm width.
In Tabelle III sind die an Papierblättern gemessenen Ergebnisse unter Verwendung von mit anderen Quaternisierungsmitteln hergestellten Harzen (Beispiele 10 bis 15) der deutschen Patentschrift 1177 824) zusammengestellt. In Table III are the results measured on paper sheets using with other quaternizing agents resins produced (Examples 10 to 15) of German Patent 1177 824).
Tabelle III1)Table III 1 )
QuaternisierungsmittelsType of
Quaternizing agent
rungsmittelQuaternization
funds
kg/2,54 cm BreiteWet tensile strength
kg / 2.54 cm width
deutschen
Patentschrift
1 177 824Example of
German
Patent specification
1 177 824
zugesetztes Harz
(Trocken/O
added resin
(Dry
') Grundgewicht aller Blätter war 18,1 ± 0,2 kg pro 19350 cm2. Blätter aus dem gleichen Stoffbrei gaben vom Filz genommen Naßzugfestigkeiten von 0,4 (ungehärtet) und 0,5 (gehärtet) kg pro 2,54 cm Breite.') Basic weight of all leaves was 18.1 ± 0.2 kg per 19,350 cm 2 . Sheets made from the same pulp gave wet tensile strengths, taken from the felt, of 0.4 (uncured) and 0.5 (cured) kg per 2.54 cm width.
Beispiel 4 der nach den Beispielen 16 bis 18 der deutschenExample 4 according to Examples 16 to 18 of the German
Patentschrift 1 177 824 erhaltenen Harze wurde zu-Patent 1 177 824 obtained resins was added
Gebleichter Kraftzellstoff wurde auf eine Schoppcr- 65 gesetzt. Sie wurde dann auf einer Handblattmaschine Riegler-Freiheit von 750 cm3 in einem Kreislauf- unter Verwendung eines geschlossenen Systems in holländer vermählen. Diese Masse wurde auf pH 9 mit Blattform gebracht, worin das Weißwasser 3CO Teile 10%iger Natriumhydroxydlösung eingestellt, und 1 % pro Million Sulfation enthielt, und auf pH 9 mitBleached kraft pulp was placed on a Schoppcr-65. It was then ground on a Riegler-Freiheit hand sheet machine of 750 cm 3 in a circuit using a closed system in Dutch. This mass was brought to pH 9 with leaf form, in which the white water adjusted to 3CO parts 10% sodium hydroxide solution, and contained 1% per million sulfate ion, and to pH 9 with
10%igerNatriumhydroxydlösungeingestellt. Die Handblätter wurden auf einem üblichen Trommeltrockner getrocknet. Ein Teil davon wurde zusätzlich während !Stunde bei 1050C gehärtet. Die Blätter wurden10% sodium hydroxide solution adjusted. The handsheets were dried on a conventional drum dryer. A part of it was additionally hardened at 105 ° C. for 1 hour. The leaves were
Stunden lang in destilliertem Wasser eingeweicht und auf Naßfestigkeit geprüft. Die Ergebnisse folgen in Tabelle IV.Soaked in distilled water for hours and tested for wet strength. The results will follow in Table IV.
deutschen Patentschrift
1 177 824Resin according to the example of
German patent specification
1 177 824
zugefügtes Harz, bezogen
auf den Trockenstoff O/
added resin, based
on the dry matter
kg/19 350 cm2 Basic weight
kg / 19,350 cm 2
kg/2,54 cmWet tensile strength
kg / 2.54 cm
gehärtet
kg/2,54 cmWet tensile strength
hardened
kg / 2.54 cm
17
1816
17th
18th
1,0
1,01.0
1.0
1.0
18,4
18,318.4
18.4
18.3
2,8
2,92.6
2.8
2.9
4,3
3,93.9
4.3
3.9
Gebleichter Sulfitweichholzzellstoff wurde in einem so pH 7 Wasser mit einem Kreislaufholländer zu einer Schopper-Riegler-Freiheit von 825 cm3 vermählen. Der Stoffbrei wurde auf 2,5 % Dichte mit Wasser von pH 7 verdünnt. Die folgenden Chemikalien wurden zu 21-Teilen des Breis unter Rühren zugefügt. *sBleached sulphite softwood pulp was ground in water with a pH of 7 with a closed-loop dutchman to a Schopper-Riegler freedom of 825 cm 3 . The pulp was diluted to 2.5% density with pH 7 water. The following chemicals were added to 21 parts of the slurry with stirring. * s
la) Ein ausreichendes Volumen an 10%iger Aluminiumsulfatlösung, um das pH des Breis auf 4,5 zu erniedrigen,la) A sufficient volume of 10% aluminum sulfate solution, to lower the pH of the pulp to 4.5,
b) 1 % (bezogen auf Trockengewicht des Stoffes) vqn einem trockenfesten Zusatz, bestehend aus einem 90: lO-Acrylamid-Acrylsäure-Mischpolymer, zugesetzt als 1 %ige wäßrige Lösung. Nach wenigen Minuten Rühren wurde ausreichend Alaunlösung zugesetzt, um das pH des Breies auf 4,5 zu erniedrigen, wie unter 1 a) angegeben. Dieses Acrylamid-Acrylsäure-Mischpolymer wurde hergestellt durch Einbringen der folgenden Stoffe in der angegebenen Reihenfolge in eine druckfeste Polymerisationsflasche: b) 1% (based on dry weight of the substance) of a dry-strength additive consisting of a 90: 10-acrylamide-acrylic acid copolymer added as a 1% aqueous solution. After a few minutes of stirring, sufficient alum solution became available added to lower the pH of the pulp to 4.5, as indicated under 1 a). This acrylamide-acrylic acid copolymer was produced by placing the following substances in the specified order in a pressure-resistant polymerisation bottle:
9,0 g umkristallisiertes Acrylamid,
185,0 g destilliertes Wasser,
1,0 g destillierte Acrylsäure,
0,5 g Isopropanol,9.0 g recrystallized acrylamide,
185.0 g of distilled water,
1.0 g of distilled acrylic acid,
0.5 g isopropanol,
5,0 ecm l%ige Lösung von K2S2O8 in *5 destilliertem Wasser.5.0 ecm 1% solution of K 2 S 2 O 8 in * 5 distilled water.
Unverzüglich nach Zugabe des Katalysators wurde der Inhalt der Flasche unter eine Stickstoffatmosphäre für mehrere Minuten gebracht. Die Flasche wurde dann verschlossen und mit einer Wasserstrahlpumpe während 1 Minute evakuiert. Stickstoff wurde bis zu einem Gesamtdruck von 3,16 kg/cma zugesetzt, und die Flasche wurde wieder evakuiert. Dieses Spülen und Evakuieren wurde noch einmal wiederholt, wonach Stickstoff bis zu einem Gesamtdruck von 2,1 kg/cm2 zugesetzt wurde. Die Polymerisationsflasche wurde dann auf eine Kippeinrichtung bei 22°C gesetzt und mehrere Tage gedreht. Die erhaltene viskose Lösung wurde mit Hydrochinon abgestoppt und eine Bestimmung der Gesamtfeststoffe zeigte, daß völlige Umwandlung zu einem polymeren Produkt erzielt worden war. Die Lösung wurde dann auf eine Konzentration von 1 Gewichtsprozent (spezifische Viskosität = 150) verdünnt und ihr pH auf 8,2 mit NaOH eingestellt. Sie wurde dann bei Γ C bis zur Verwendung gelagert.Immediately after the addition of the catalyst, the contents of the bottle were placed under a nitrogen atmosphere for several minutes. The bottle was then closed and evacuated with a water jet pump for 1 minute. Nitrogen was added to a total pressure of 3.16 kg / cm a and the bottle was again evacuated. This purging and evacuation was repeated once more, after which nitrogen was added to a total pressure of 2.1 kg / cm 2 . The polymerization bottle was then placed on a tilting device at 22 ° C. and rotated for several days. The resulting viscous solution was quenched with hydroquinone and a total solids determination indicated that complete conversion to a polymeric product had been achieved. The solution was then diluted to a concentration of 1 percent by weight (specific viscosity = 150) and its pH was adjusted to 8.2 with NaOH. It was then stored at Γ C until used.
lc) 1% (bezogen auf Trockengewicht des Stoffes) eines Polyamid-Epichlorhydrin-Kondensationsproduktes als wäßrige Lösung. Dieses Kondensationsprodukt wurde nach folgendem Verfahren hergestellt. Zu einer Mischung von 1914 g Triäthylentetramin und 600 g Wasser wurden 1740 g Adipinsäure in mehreren Anteilen zugesetzt, wobei das Auflösen jedes Anteils abgewartet wurde, bevor der nächste zugesetzt wurde. Das erhaltene Gemisch wurde dann auf 195 bis 200° C während lx/2 Stunden erwärmt, und Wasser wurde stetig während des gesamten Erhitzens abdestilliert. Die Mischung wurde dann auf 140° C unter Vakuum abgekühlt, und 3 1 80° C warmes Wasser wurden vorsichtig zugesetzt. Das Polyamidprodukt hatte einen Gesamtfeststoff gehalt von 54,4% und eine Säurezahl von 3,6. Wasser wurde zum Verdünnen von 2162 g des Produktes auf ein Gesamtgewicht von 10 751 g zugegeben. Die wäßrige Lösung wurde gerührt und auf 45°C erwärmt. In diesem Zustand wurde der Zusatz von 1025 g Epichlorhydrin begonnen. Der Zusatz wurde zu der Zeit beendet, als die Temperatur 60° C erreichte. Die Mischung wurde dann zwischen 60 und 70° C gehalten, bis ihre Viskosität auf der Gardner-Holdt-Skala den Wert E erreichte. Dann wurden 9 1 Wasser und 250 ecm 3,7 %ige Salzsäure zugesetzt. Das Endprodukt hatte ein pH von 5,75 und einen Gesamtfeststoffgehalt von 11,0%.lc) 1% (based on the dry weight of the substance) of a polyamide-epichlorohydrin condensation product as an aqueous solution. This condensation product was prepared by the following procedure. To a mixture of 1914 g of triethylenetetramine and 600 g of water, 1740 g of adipic acid were added in several portions, each portion waiting to dissolve before the next was added. The resulting mixture was then heated to 195 to 200 ° C over 1 x / 2 hours, and water was steadily distilled off throughout the heating. The mixture was then cooled to 140 ° C under vacuum and 3 liters of 80 ° C water was carefully added. The polyamide product had a total solids content of 54.4 percent and an acid number of 3.6. Water was added to dilute 2162 grams of the product to a total weight of 10,751 grams. The aqueous solution was stirred and heated to 45 ° C. In this state, the addition of 1025 g of epichlorohydrin was started. The addition was stopped by the time the temperature reached 60 ° C. The mixture was then held between 60 and 70 ° C until its viscosity reached E on the Gardner-Holdt scale. Then 9 l of water and 250 ecm of 3.7% hydrochloric acid were added. The final product had a pH of 5.75 and a total solids content of 11.0%.
Id) 1% des Polyamid-Epichlorhydrin-Kondensationsproduktes
von Ic) (bezogen auf das Trockengewicht des Stoffs). Nach wenigen Minuten
Rühren wurde ein gleiches Gewicht des Acrylamid-Acrylsäure-Mischpolymers
von 1 b) zu dem Brei zugesetzt. Der pH-Wert des Endbreies sowohl für 1 c) wie 1 d) war etwa 7,0.
Alle Breimuster wurden auf 0,25% Dichte mit Wasser von pH 7 verdünnt und dann weiter auf
eine Konzentration im Stoffauflaufkasten von 0,025% verdünnt, um Handblätter von 18 kg
Grundgewicht (24 · 35-500 Blattries) unter Verwendung einer Blattmaschine zu bilden. Ein geschlossenes
Weißwassersystem wurde benutzt. Die gebildeten Blätter wurden naß auf 35 bis 45%
Feststoff gehalt ausgepreßt und dann bei 121 "C auf einem Dampftrommeltrockner getrocknet.
Nach dem Konditionieren für mehrere Tage bei 23°C und 50% relativer Feuchtigkeit wurden die
Blätter in der gleichen Umgebung auf verschiedenePapierfestigkeitseigenschaften
unter Ver-Id) 1% of the polyamide-epichlorohydrin condensation product from Ic) (based on the dry weight of the substance). After a few minutes of stirring, an equal weight of the acrylamide-acrylic acid mixed polymer from 1 b) was added to the slurry. The pH of the final slurry for both 1 c) and 1 d) was about 7.0.
All pulp swatches were diluted to 0.25% density with water of pH 7 and then further diluted to a headbox concentration of 0.025% to form handsheets of 18 kg basis weight (24 x 35-500 sheet bars) using a sheet machine. A closed white water system was used. The resulting sheets were wet pressed to 35 to 45% solids and then dried at 121 "C on a steam drum dryer. After conditioning for several days at 23 ° C and 50% relative humidity, the sheets were tested in the same environment for various paper strength properties under Ver -
wendung von Standardprüfeinrichtungen geprüft. Die Festigkeitswerte wurden auf 18 kg/Riesgrundgewicht unter Verwendung der linearen Beziehung S = kB korrigiert, worin S die Festigkeitseigenschaften und B das Blattgrundgewicht darstellt. Die Ergebnisse folgen in Tabelle V. "using standard testing equipment. Strength values were corrected to 18 kg / ream basis weight using the linear relationship S = kB , where S is strength properties and B is sheet basis weight. The results follow in Table V. "
Versuchattempt
Trockenfestigkeitseigenschaften (korrigiert zu 18 kg/R. Grundgewicht)Dry strength properties (corrected to 18 kg / r. Basis weight)
Elemendorf-Reißversuch g pro BlattElemendorf tear test g per sheet
Mullen-Berstfestigkeit kg/cm2 Mullen burst strength kg / cm 2
Zunahme in derIncrease in the
Reiß-Berst-BlattfestigkeitTear-burst blade strength
gegen Kontrolle1)against control 1 )
Ungehärtete Naßzugfestigkeit nach 2 Stunden Einweichen in destilliertem WasserUncured wet tensile strength after soaking in distilled water for 2 hours
la)
Ib)
Ic)
Id)la)
Ib)
Ic)
Id)
86
6086
60
74
5474
54
TAPPI, 40, S. 499, Juli 1947.TAPPI, 40, p. 499, July 1947.
Kontrollecontrol
16,416.4
4,54.5
20,020.0
Nicht geprüft 0,7 kg/2,54 cmNot tested 0.7 kg / 2.54 cm
1,51.5
2,92.9
Die obigen Werte zeigen, daß, wenn ein kationisches Polyamid-Epichlorhydrin-Harz der hier offenbarten Art mit dem Acrylsäuremischpolymer-Trockenfestigkeitszusatz verwendet wird, eine Verbesserung in der gesamten Reiß-Berstfestigkeit von 20% im Vergleich mit der Alaunkontrolle erzielt wurde, während das Harz allein eine Verbesserung von 4,5 % und der Alaun plus dem Trockenfestigkeitszusatz eine Verbesserung von 16,4% ergab.The above data indicate that when a cationic polyamide-epichlorohydrin resin is the one disclosed herein Type used with the acrylic acid copolymer dry strength additive, an improvement in that overall tear burst strength of 20% compared to the alum control was achieved while the Resin alone an improvement of 4.5% and the alum plus dry strength additive an improvement of 16.4%.
Die folgenden Beispiele 6 bis 9 erläutern den Einsatz der erfindungsgemäß verwendeten kationischen Harze in Verbindung mit der Einverleibung von wasserlöslichen Überzugs-, Imprägnierungs- und Leimungsmitteln in Papier u. dgl.The following Examples 6 to 9 illustrate the use of the cationic compounds used according to the invention Resins in connection with the incorporation of water-soluble coating, impregnating and sizing agents in paper and the like
Eine Ketendimerzusammenstellung wurde in folgender Weise hergestellt: In einen Mischer wurden 10 Teile einer gereinigten Kieselsäure niedriger Dichte gegeben. Das Mischgefäß wurde in einem Dampfbad auf 50° C erwärmt, und 10 Teile des geschmolzenen Alkylketendimers, hergestellt aus einer Mischung von Myristin- und Palmitinsäure (Schmelzpunkt etwa 33° C), wurden tropfenweise zu der stark gerührten Kieselerde zugesetzt. Das Produkt wurde aus dem Mischer in Form eines freifließenden Pulvers entfernt, bestehend aus dem auf Kieselerde getragenen Ketendimer in einem Gewichtsverhältnis von 1:1.A ketene dimer assembly was prepared in the following manner: Into a mixer Added 10 parts of a purified low density silica. The mixing vessel was in a steam room heated to 50 ° C, and 10 parts of the molten alkyl ketene dimer made from a mixture of Myristic and palmitic acids (melting point about 33 ° C) were added dropwise to the vigorously stirred Silica added. The product was removed from the mixer in the form of a free flowing powder, consisting of the ketene dimer supported on silica in a weight ratio of 1: 1.
Ein 1 %iger wäßriger Brei der so hergestellten Ketendimerzusammenstellung wurde unter mildem Schlagen in einem Mischer zubereitet. Verschiedene Anteile dieses Breies wurden je 3 Minuten in einem Mischer mit 500 ecm gebleichtem Sulfitzellstoff von 2,5 % Dichte verarbeitet, welcher zuvor mit Schopper-Riegler-Freiheit von 750 cm3 in Leitungswasser mit einem Holländer hergestellt worden war. Die Stoff-Brei-Mischung wurde in jedem Fall auf 51 (0,25 % Dichte) mit Leitungswasser verdünnt, und dann wurden verschiedene Mengen einer l%igen Feststofflösung verschiedener Zurückhalte-Hilfsstoffe zugesetzt und gemischt. Für jedes Blatt wurden 450 cm3 jedes Stoffbreigemisches auf 1,11 (0,1% Dichte) verdünnt zur Blattbildung auf einem 100-Maschen-Sieb aus nichtrostendem Stahl in einer kreisförmigen Blattform von 15,5 cm Durchmesser. Die Blätter wurden zwischen Filzen gepreßt und 60 Sekunden auf einem dampferhitzten Trommeltrockner bei 115°C getrocknet. Für das erste Blatt wurde Leitungswasser zur Verdünnung auf 0,1% Dichte benutzt. Bei den übrigen Blättern wurde Weißwaser für die Verdünnung verwendet. In dieser Weise hergestellte Blätter hatten ein Grundgewicht von etwa 18 kg pro 19 350 cm2. Die Leimung in den Blättern wurde mit einem Photometer gemessen unter Verwendung 20%iger Milchsäuretinte, nachdem die Blätter 48 Stunden bei Raumtemperatur gealtert waren. Die Ergebnisse in Tabelle 6 sind Durchschnittszeiten (5 Blätter geprüft in jeder Reihe) gegen 85% des ursprünglichen Reflexionsvermögens.A 1% aqueous slurry of the ketene dimer composition so prepared was prepared in a mixer with gentle whipping. Different proportions of this pulp were processed for 3 minutes each in a mixer with 500 ecm of bleached sulfite pulp of 2.5% density, which had previously been prepared with a Schopper-Riegler-Freiheit of 750 cm 3 in tap water with a Dutchman. The pulp mixture was diluted to 51% (0.25% density) with tap water in each case and then various amounts of a 1% solids solution of various retention aids were added and mixed. Were, for each blade 450 cm 3 each Stoffbreigemisches to 1.11 (0.1% density) diluted to the sheet formation on a 100-mesh stainless steel screen in a circular sheet form of 15.5 cm in diameter. The sheets were pressed between felts and dried on a steam-heated drum dryer at 115 ° C. for 60 seconds. For the first sheet, tap water was used to dilute it to 0.1% density. White water was used for the dilution of the remaining leaves. Sheets made in this way had a basis weight of about 18 kg per 19,350 cm 2 . The sizing in the leaves was measured with a photometer using 20% lactic acid ink after the leaves were aged for 48 hours at room temperature. The results in Table 6 are average times (5 sheets tested in each row) versus 85% of the original reflectivity.
τι ic 1 tYimArtKetene dimer
τι ic 1 tYimArt
stellung/.UoallllllCithaben
position
*) Bei 100 Sekunden war das Reflexionsvermögen immer noch über 85% des ursprünglichen und gleich den angegebenen Prozenten.*) At 100 seconds the reflectivity was still over 85% of the original and equal to the percentages indicated.
Das im Beispiel 6 verwendete Epichlorhydrin-Polyamid-Harz war wie folgt hergestellt: Zu 319 g Triäthylentetramin und 100 g auf 123° C erwärmtem Wasser wurden 290 g Adipinsäure in kleinen Anteilen zugegeben. Nach Beendigung des Säurezusatzes wurde die Mischung auf etwa 190° C erhitzt und auf 190 bis 205° C während etwa 105 Minuten gehalten. Nach dieser Zeit wurde die Wärmequelle entfernt und der Druck über dem Harz soweit wie möglich ohne überschüssiges Schäumen während einer Zeit von 10 Minuten verringert. Dann wurden 500 cm3 Wasser zugesetzt, um eine fließfähige Lösung mit 49,8% Feststoffen zu ergeben. 63 g dieser Lösung wurden mit 225 cm3 Wasser verdünnt und auf 50° C erwärmt. Die Wärmequelle wurde entfernt und der Zusatz von 22 g Epichlorhydrin begonnen und mit einer Geschwindigkeit aufrechterhalten, welche die Temperatur der Lösung auf etwa 55° C erhielt. Der Zusatz erforderte 3 Minuten. Die Mischung wurde auf etwa 60°C er-The epichlorohydrin-polyamide resin used in Example 6 was prepared as follows: 290 g of adipic acid were added in small portions to 319 g of triethylenetetramine and 100 g of water heated to 123.degree. After the addition of acid was complete, the mixture was heated to about 190 ° C and held at 190-205 ° C for about 105 minutes. After this time the heat source was removed and the pressure above the resin was reduced as much as possible without excessive foaming over a period of 10 minutes. Then, 500 cm 3 of water is added to give a flowable solution with 49.8% solids. 63 g of this solution were diluted with 225 cm 3 of water and heated to 50 ° C. The heat source was removed and the addition of 22 grams of epichlorohydrin commenced and maintained at a rate which maintained the temperature of the solution at about 55 ° C. The addition took 3 minutes. The mixture was heated to about 60 ° C
wärmt und auf etwa 60 bis 66° C für 70 Minuten gehalten, während welcher Zeit die Viskosität der Lösung auf E (Gardner-Skala) anstieg. In diesem Zeitpunkt wurden 225 ecm Wasser zugesetzt und das pH auf 5 mit Salzsäure eingestellt. Die Endviskosität war etwa C (Gardner-Skala) und der Gesamtfeststoff gehalt etwa 8 bis 9,5%.warms up and held at around 60 to 66 ° C for 70 minutes, during which time the viscosity of the solution rose to E (Gardner scale). At this point in time 225 ecm of water were added and the pH was adjusted to 5 with hydrochloric acid. The final viscosity was about C (Gardner scale) and the total solids content about 8 to 9.5%.
Die im Beispiel 6 verwendete Stärke ist eine kationische Stärke (modifizierte Maisstärke mit einem Stickstoffgehalt von etwa 0,25 %).The starch used in Example 6 is a cationic starch (modified corn starch with a Nitrogen content of about 0.25%).
Die durchschnittlichen Mullenberstfestigkeiten vonThe average Mullen Burst Strengths of
Das Verfahren vom Beispiel 6 wurde mit folgenden gleichem Papier, jedoch hergestellt ohne das Epichlor-Abänderungen wiederholt. 15 hydrin-Polyamid-Harz, waren 0,22 kg/cm2.The procedure of Example 6 was repeated with the following identical paper, but produced without the epichloro alteration. 15 hydrin-polyamide resin, was 0.22 kg / cm 2 .
Polyamid-Harz
%Epichlorohydrin
Polyamide resin
%
Zeit/SekundenPhotometer
Time / seconds
Berstfestigkeit
kg/cm2 Mullen
Burst strength
kg / cm 2
0,5
ίο 0,25
0,1251
0.5
ίο 0.25
0.125
25
11
325th
25th
11
3
0,86
0,45
0,290.86
0.86
0.45
0.29
1. Ungebleichter Kraftzellstoff, vermählen auf Schopper-Riegler-Freiheit von 750 cm3, wurde verwendet. 1. Unbleached kraft pulp, ground to a Schopper-Riegler clearance of 750 cm 3 , was used.
2. 5 cm3 einer 0,15%igen wäßrigen Alkylketendimeremulsion (0,5% Alkylketendimer, bezogen auf den Trockenstoff) wurden zu jedem Teil des Stoffs nach Verdünnung auf 0,25% Dichte zugesetzt. Die wäßrige Ketendimeremulsion wurde aus einer Mischung von 5 Teilen Alkylketendimer, hergestellt aus einer Mischung von PaI-mitin- und Stearinsäure, und 1 Teil Hexaoleat eines Sorbitoläthylenoxyd-Komplexes zubereitet.2. 5 cm 3 of a 0.15% aqueous alkyl ketene dimer emulsion (0.5% alkyl ketene dimer on dry matter) was added to each portion of the fabric after dilution to 0.25% density. The aqueous ketene dimer emulsion was prepared from a mixture of 5 parts of alkyl ketene dimer, prepared from a mixture of palmitic and stearic acid, and 1 part of hexaoleate of a sorbitol ethylene oxide complex.
3. Nach 2 bis 3 Minuten mildem Rühren wurden verschiedene Mengen (10 cm3, 5 cm3, 2,3 cm3 und 1,25 cm3, welche 1%, »/2%, XU% und \% Harz entsprechen, bezogen auf den Trockenzellstoff) einer l,25%igen Feststofflösung des Epichlorhydrin-Polyamid-Harzes vom Beispiel 6 zugesetzt.3. After 2 to 3 minutes of gentle stirring, different amounts (10 cm 3 , 5 cm 3 , 2.3 cm 3 and 1.25 cm 3 , which correspond to 1%, 1/ 2 %, X U% and \% resin) were added , based on the dry pulp) to a 1.25% solids solution of the epichlorohydrin-polyamide resin from Example 6 was added.
Die Ergebnisse der Photometer-Leimungsprüfung mit 20%iger Milchsäuretinte und die Mullen-Berstfestigkeiten nach 24 Stunden Einweichen in Wasser folgen in Tabelle VII.The results of the photometer sizing test with 20% lactic acid ink and the Mullen burst strengths after soaking in water for 24 hours follow in Table VII.
Polyamid-Harz
%Epichlorohydrin
Polyamide resin
%
Zeit/SekundenPhotometer
Time / seconds
Berstfestigkeit
kg/cm2 Mullen
Burst strength
kg / cm 2
0,5
0,25
0,1251
0.5
0.25
0.125
196
3
0140
196
3
0
0,79
0,49
0,281.12
0.79
0.49
0.28
1,25 g Ton wurden zu 5 1 eines gebleichten Kraft-Zellstoffs von 0,25% Dichte zugesetzt. Dieser Stoff war bei etwa 5 % Dichte in Leitungswasser auf Schopper-Riegler-Freiheit von 750 cm3 vermählen worden. Dieser Stoff wurde auf 0,25 % mit Leitungswasser verdünnt. Nach gründlichem Vermischen des Stoffs und des Tons wurden 25 cm3 eines 0,125 %igen Epichlorhydrin-Polyamid-Harzes, hergestellt wie im Beispiel 6 beschrieben, zugesetzt. Dies entspricht 0,25% Harz, bezogen auf den Trockenstoff. Fünf Blätter wurden wie im Beispiel 6 hergestellt. Ein gleicher Satz von fünf Blättern wurde ohne das Harz gefertigt. Das Weißwasser für jede Reihe wurde durch besondere Filterpapiere filtriert, welche nach Konditionieren während 24 Stunden in einem Raum von konstanter Temperatur und konstanter Feuchtigkeit gewogen worden waren. Die Filterpapiere mit dem Weißwasserfeinen wurden getrocknet, konditioniert und wieder gewogen. Das Gewicht des Feinen dividiert durch das Gewicht des Feinen plus dem Gewicht der Blätter in jeder Reihe, multipliziert mit 100, gibt die Prozente von für fünf Blätter verwendetem Stoff und Ton, welche durch das Papierherstellungssieb hindurchgingen. Der Aschegehalt des ersten, dritten und fünften Blatts in jeder Reihe wurde bestimmt. Die Ergebnisse folgen in Tabelle IX.1.25 grams of clay was added to 5 liters of bleached Kraft pulp of 0.25% density. This substance was ground at a density of about 5% in tap water to a Schopper-Riegler clearance of 750 cm 3 . This material was diluted to 0.25% with tap water. After thoroughly mixing the fabric and the clay, 25 cm 3 of a 0.125% epichlorohydrin-polyamide resin, prepared as described in Example 6, was added. This corresponds to 0.25% resin, based on the dry matter. Five sheets were made as in Example 6. An identical set of five sheets was made without the resin. The white water for each row was filtered through special filter papers which, after conditioning, were weighed for 24 hours in a constant temperature and constant humidity room. The filter papers with the white water fine were dried, conditioned and weighed again. The weight of the fineness divided by the weight of the fineness plus the weight of the sheets in each row multiplied by 100 gives the percent of fabric and clay used for five sheets that passed through the papermaking screen. The ash content of the first, third and fifth sheets in each row was determined. The results are shown in Table IX.
ZurückhaltehilfeRestraint aid
o/ /oO/ /O
durch das Sieb
hindurchgegangenes
Feinesthrough the sieve
passed through
Fine
Die durchschnittlichen Mullen-Berstfestigkeiten von gleichem Papier, jedoch hergestellt ohne das Epichlorhydrin-Polyamid-Harz, waren 0,22 kg/cm2.The average Mullen burst strengths of the same paper but made without the epichlorohydrin-polyamide resin were 0.22 kg / cm 2 .
Das Verfahren vom Beispiel 7 wurde mit der Abänderung verwendet, daß 5 cm3 einer Wachsemulsion mit 1,25% Feststoffgehalt an Stelle der 5 cm3 der 0,15%igen Alkylketenemulsion eingesetzt wurden. Dies sind 0,4% Wachsemulsion-Feststoff, bezogen auf den Trockenstoff. Die Wachsemulsion war ein handelsübliches Produkt, welches 45% Gesamtfeststoffe und 43,4% völlig raffiniertes Paraffinwachs enthält.The procedure of Example 7 was used with the modification that 5 cm 3 of a wax emulsion with 1.25% solids content were used in place of the 5 cm 3 of the 0.15% strength alkyl ketene emulsion. This is 0.4% wax emulsion solids, based on the dry matter. The wax emulsion was a commercial product containing 45% total solids and 43.4% fully refined paraffin wax.
Die Ergebnisse der photometrischen Leimungsprüfung mit 20% Milchsäuretinte und die Mullenberstfestigkeitsprüfung nach 24 Stunden Einweichen ergeben sich aus Tabelle VIII.The results of the photometric sizing test with 20% lactic acid ink and the Mullen burst strength test after 24 hours of soaking are shown in Table VIII.
0,25%Epichlor-0.25% epichlor
hydrin-Polyamid-Harz ..
Keine hydrin polyamide resin.
None
7,70
9,727.70
9.72
% Asche
1. Blatt I 3. Blatt I 5. Blatt% Ashes
1st sheet I 3rd sheet I 5th sheet
3,4
1,23.4
1.2
4,0
1,54.0
1.5
Handblätter wurden hergestellt aus einer Mischung von 75% Glasfasern und 25% gebleichtem Kraftzellstoff. Sie wurden in einer kreisförmigen Blattform von 15 cm Durchmesser geformt. Ein Brei wurde aus 2,25 g Glasfasern plus 0,75 g gebleichtem Kraftzellstoff in 300 ecm Wasser hergestellt. Dieser wurde dann 2 Minuten in einem Mischer gerührt. Der pH-Wert wurde auf 9,5 mit 10%iger NaOH eingestellt und 360 g einer 0,1 %igen Lösung des Harzes, hergestelltHand sheets were made from a blend of 75% glass fiber and 25% bleached kraft pulp. They were shaped into a circular leaf shape 15 cm in diameter. A pulp was made 2.25 g of glass fibers plus 0.75 g of bleached kraft pulp in 300 ecm of water. This one then became Stirred in a mixer for 2 minutes. The pH was adjusted to 9.5 with 10% NaOH and 360 g of a 0.1% solution of the resin
wie im Beispiel 1 der deutschen Patentschrift 1177 824 (12% Feststoffe, bezogen auf Trockenfasern), zugesetzt. Nach 2 Minuten Rühren wurde der Brei zu einem Blatt geformt, gepreßt und trommelgetrocknet. Ein gebleichtes Blatt wurde hergestellt mit dem Unterschied, daß kein Harz zugesetzt wurde. Beide Blätter wurden 30 Minuten in destilliertem Wasser eingeweicht und dann mit einem Mullen-Berstfestigkeitsprüfer auf Naßfestigkeit geprüft. Die Ergebnisse folgen in Tabelle XII.as in example 1 of German patent specification 1177 824 (12% solids based on dry fibers) added. After stirring for 2 minutes the slurry turned to formed into a sheet, pressed and drum dried. A bleached sheet was made with the difference, that no resin was added. Both sheets were soaked in distilled water for 30 minutes and then tested for wet strength with a Mullen Burst Tester. The results follow in Table XII.
1414th
/o/O
zugesetztes Harz, bezogen auf Fasertrockengewichtadded resin based on dry fiber weight
12 012 0
Naßfestigkeit (Nullen) kg/cm2 Wet strength (zeros) kg / cm 2
0,350.35
Zu schwach für die PrüfungToo weak for the exam
Claims (5)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68208957A | 1957-09-05 | 1957-09-05 | |
| US682086A US2926116A (en) | 1957-09-05 | 1957-09-05 | Wet-strength paper and method of making same |
| US69493057A | 1957-11-07 | 1957-11-07 | |
| US694909A US3049469A (en) | 1957-11-07 | 1957-11-07 | Application of coating or impregnating materials to fibrous material |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1546369A1 DE1546369A1 (en) | 1970-05-21 |
| DE1546369B2 DE1546369B2 (en) | 1974-04-04 |
| DE1546369C3 true DE1546369C3 (en) | 1974-11-21 |
Family
ID=27505392
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEH34226A Pending DE1177824B (en) | 1957-09-05 | 1958-09-02 | Process for the production of water-soluble condensates based on polyamides and epichlorohydrin |
| DE1546369A Expired DE1546369C3 (en) | 1957-09-05 | 1958-09-02 | Process for making paper, paperboard and the like with improved wet strength. Eliminated from: 1177824 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEH34226A Pending DE1177824B (en) | 1957-09-05 | 1958-09-02 | Process for the production of water-soluble condensates based on polyamides and epichlorohydrin |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US2926116A (en) |
| DE (2) | DE1177824B (en) |
| FR (1) | FR1265829A (en) |
| GB (1) | GB865727A (en) |
| NL (2) | NL110447C (en) |
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| US3049469A (en) * | 1957-11-07 | 1962-08-14 | Hercules Powder Co Ltd | Application of coating or impregnating materials to fibrous material |
| DE748253C (en) * | 1938-06-10 | 1944-10-30 | Process for the production of deformable high molecular weight polyamides | |
| DE758619C (en) * | 1940-07-19 | 1953-01-05 | Ig Farbenindustrie Ag | Process for the production of polyamides |
| GB610311A (en) * | 1944-07-28 | 1948-10-14 | Sidney James Allen | Improvements in the production of basic polyamides |
| US2595935A (en) * | 1946-08-03 | 1952-05-06 | American Cyanamid Co | Wet strength paper and process for the production thereof |
| US2601597A (en) * | 1946-09-06 | 1952-06-24 | American Cyanamid Co | Application of dispersed coating materials to cellulosic fibers |
| US2969302A (en) * | 1957-02-14 | 1961-01-24 | Nalco Chemical Co | Method of making paper |
| NL231136A (en) * | 1957-09-05 |
-
0
- NL NL231136D patent/NL231136A/xx unknown
- NL NL110447D patent/NL110447C/xx active
-
1957
- 1957-09-05 US US682086A patent/US2926116A/en not_active Expired - Lifetime
-
1958
- 1958-08-21 GB GB26945/58A patent/GB865727A/en not_active Expired
- 1958-09-02 DE DEH34226A patent/DE1177824B/en active Pending
- 1958-09-02 DE DE1546369A patent/DE1546369C3/en not_active Expired
- 1958-09-05 FR FR38672A patent/FR1265829A/en not_active Expired
-
1969
- 1969-01-17 US US792161*A patent/US3483077A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007059736A1 (en) * | 2007-12-12 | 2009-06-18 | Omya Development Ag | Surface mineralized organic fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1546369A1 (en) | 1970-05-21 |
| US3483077A (en) | 1969-12-09 |
| DE1546369B2 (en) | 1974-04-04 |
| DE1177824B (en) | 1964-09-10 |
| NL110447C (en) | |
| FR1265829A (en) | 1961-07-07 |
| NL231136A (en) | |
| US2926116A (en) | 1960-02-23 |
| GB865727A (en) | 1961-04-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| SH | Request for examination between 03.10.1968 and 22.04.1971 | ||
| C3 | Grant after two publication steps (3rd publication) |