EP2126209A1 - Mixtures of paper gluing agents - Google Patents
Mixtures of paper gluing agentsInfo
- Publication number
- EP2126209A1 EP2126209A1 EP07848052A EP07848052A EP2126209A1 EP 2126209 A1 EP2126209 A1 EP 2126209A1 EP 07848052 A EP07848052 A EP 07848052A EP 07848052 A EP07848052 A EP 07848052A EP 2126209 A1 EP2126209 A1 EP 2126209A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixtures
- acid
- component
- water
- monomers
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 238000004026 adhesive bonding Methods 0.000 title abstract 9
- 239000006185 dispersion Substances 0.000 claims abstract description 94
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000004094 surface-active agent Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 124
- -1 alkyl ketene dimer Chemical compound 0.000 claims description 58
- 238000004513 sizing Methods 0.000 claims description 56
- 239000000123 paper Substances 0.000 claims description 54
- 229920002472 Starch Polymers 0.000 claims description 50
- 235000019698 starch Nutrition 0.000 claims description 49
- 239000008107 starch Substances 0.000 claims description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- 239000004908 Emulsion polymer Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 25
- 125000002091 cationic group Chemical group 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000084 colloidal system Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 16
- 150000001298 alcohols Chemical class 0.000 claims description 13
- 125000000129 anionic group Chemical group 0.000 claims description 13
- 230000001804 emulsifying effect Effects 0.000 claims description 12
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 239000003945 anionic surfactant Substances 0.000 claims description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- 229920000881 Modified starch Polymers 0.000 claims description 10
- 235000019426 modified starch Nutrition 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 7
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 7
- 229920001567 vinyl ester resin Polymers 0.000 claims description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 claims description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 9
- 238000004945 emulsification Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 description 39
- 229920001577 copolymer Polymers 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 description 13
- 239000003381 stabilizer Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000003999 initiator Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
- 239000004815 dispersion polymer Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012966 redox initiator Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229920006320 anionic starch Polymers 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 4
- 229920000945 Amylopectin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000002432 hydroperoxides Chemical class 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000011111 cardboard Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920001592 potato starch Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical group OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
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- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/18—Homopolymers or copolymers of nitriles
- C09J133/20—Homopolymers or copolymers of acrylonitrile
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
Definitions
- the invention relates to paper size mixtures of a water-dispersed reactive size and a polymer.
- the dispersing of the alkyldiketenes can additionally be carried out in the presence of lignosulfonic acid, condensates of naphthalenesulfonic acid and formaldehyde, polymers containing styrenesulfonic acid groups or their alkali metal and / or ammonium salts.
- the average particle diameter of the water-dispersed alkyldiketenes is 0.5 to 2.5 ⁇ m, preferably 0.8 to 1.5 ⁇ m. According to the information in the examples, it is always above 1 ⁇ m.
- the mixtures are prepared by ketendispersion an alkyl di- with a polymer dispersion mixed or in that one emulsified alkyldiketenes at a temperature of at least 70 0 C in a mixture, the finely divided aqueous suspensions of cationic starch having an amylopectin content of at least 98%, and , aqueous polymer dispersions.
- Such mixtures consist of two different types of particles, namely particles of alkyl diketene and particles of emulsion polymer.
- WO 2004/037867 discloses aqueous polymer dispersions comprising alkyldiketenes which are obtainable by miniemulsion polymerization of hydrophobic monoethylenically unsaturated monomers in the presence of alkylketene dimers.
- a single particle dispersed in water contains both alkyl ketene dimer and hydrophobic polymer.
- the average particle diameter is in the range from 50 to 500 nm, preferably 50 to 200 nm.
- Correspondingly constructed polymer dispersions which contain alkenylsuccinic anhydrides instead of alkylketene dimers are known from WO 2005/070912. They are prepared by polymerizing hydrophobic monomers in the manner of a miniemulsion polymerization in the presence of alkenylsuccinic anhydrides and optionally additionally alkylketene dimers.
- WO 2004/022847 discloses the use of polymers containing vinylamine units as a promoter for the size sizing of paper.
- aqueous dispersions which contain stearyl diketene, cationic starch and polyvinylamine.
- the subject of the earlier EP application 06 115 714.5 is a process for the preparation of at least one lipophilic active substance-containing aqueous polymer dispersions by emulsion polymerization of ethylenically unsaturated monomers in an aqueous medium in the presence of at least one lipophilic active ingredient, wherein
- At least one lipophilic active ingredient having a water solubility of at most 5 g / l (determined at 25 ° C and 1013 mbar) and a melting point below 130 0 C, in an aqueous solution containing at least one dispersion stabilizer, with formation an aqueous dispersion of the active ingredient having an average particle size of at most 1000 nm, preferably at most 500 nm, emulsified and
- the particles of the aqueous polymer dispersions contain, for example, when using alkyl ketene dimer as the active ingredient both alkyl ketene dimer and emulsion polymer and have an average particle diameter of at most 1000 nm.
- the invention has for its object to provide other products for paper sizing available, which cause the fastest possible training of sizing.
- the object is achieved according to the invention with bleach mixtures of a water-dispersed reactive sizing agent and a polymer, wherein they are obtainable by mixing
- A an aqueous dispersion of a reactive sizing agent whose dispersed particles have an average particle diameter of less than 500 nm, wherein the dispersion is obtainable by emulsifying at least one reactive sizing agent in water in the presence of at least one surfactant, and (b) at least one emulsion polymer and / or at least one water-soluble polymer which does not disperse reactive wetting agents and / or a water-dispersible polymer.
- component (a) of the mixtures is an aqueous dispersion of a reactive sizing agent whose dispersed particles have an average particle diameter of at most 300 nm.
- Component (a) of the mixtures contains, as a reactive sizing agent, an aqueous aqueous dispersion of an alkyl ketene dimer and / or an alkenyl succinic anhydride having an average particle size of the dispersed particles of, for example, 30 to 300 nm.
- the weight ratio of components (a) and (b) in the mixture is, for example, 1: 100 to 100: 1 and is preferably in the range from 1:20 to 20: 1. Particularly preferred are paper size mixtures which are used as component
- (B) at least one emulsion polymer having a mean particle diameter of 100 nm highest.
- Suitable alkyl ketene dimers are preferably C 4 - to C 22 -alkyl- or alkenyl-diketenes. They are prepared for example from the corresponding carboxylic acid chlorides by elimination of hydrogen chloride with tertiary amines.
- the ketene dimers which can be used according to the invention can carry saturated or unsaturated, branched or cyclic hydrocarbon radicals.
- alkyl ketene dimers examples include tetradecyldiketene, hexadecyldiketene, octadecyldiketene, docosyldiketen, palmityldiketen, oleyldiketen, stearyldiketen and behenyldiketen.
- Alkenylsuccinic anhydrides are described in detail in, for example, US Pat. No. 3,102,064, EP-A 0 609 879 and EP-A 0 593 075. All alkenylsuccinic anhydrides which have hitherto been described in the literature as engine size agents for paper are also suitable according to the invention as active ingredient, either alone or in combination with alkyldiketenes.
- Suitable alkenylsuccinic anhydrides in the alkenyl group contain an alkyl radical having at least 6 C atoms, preferably a C 4 - to C 24 -olefin radical.
- Particularly preferred alkenyl succinic anhydrides contain 16 to 22, usually 16 to 18 C atoms in the alkenyl group.
- Alkenylsuccinic anhydrides are accessible for example from ⁇ -olefins, which are first isomerized. In this case, a mixture of different isomers is obtained, which is then reacted with maleic anhydride in the manner of an ene reaction to succinic anhydrides.
- Alkenylsuccinic anhydrides are prepared according to EP-A 0 593 075 by reaction of propylene or n-butylene oligomers with maleic anhydride.
- Examples of this group of reactive sizing agents are decenylsuccinic anhydride, dodecenylsuccinic anhydride, octene nylbernsteinklareanhydrid and n-Hexadecenylbernsteinklahydrid.
- the individual isomeric succinic anhydrides can have different sizing effect.
- 2- and 3-hexadecenyl succinic anhydrides are not as effective as mass sizing agents as the isomeric 4-, 5-, 6-, 7- and 8-hexadecenyl succinic anhydrides.
- the eligible reactive sizes are dispersed in water for the preparation of component (a) of the mixtures according to the invention. They are preferably first melted and then emulsified as a melt in water in the presence of a surfactant which acts as a dispersion stabilizer.
- the emulsifying of the reactive sizing agent can be carried out, for example, by high-pressure emulsification in the devices known for this purpose, with the aid of the action of ultrasound or by the action of strong shearing forces, for example with the aid of an Ultra-Turrax® device.
- the temperature of the system may be from 0 to 130 ° C., preferably up to 100 ° C.
- Most of the reactive size agents are emulsified in the temperature range of 5 to 95 0 C in water containing at least one surfactant. If temperatures above 100 ° C. are used, the emulsification step is carried out under elevated pressure in pressure-tight apparatus.
- the temperature should be at least 5 0 C, preferably at least 10 0 C above the melting point or above the incipient softening range of the respective reactive sizing agent.
- the resultant oil-in-water emulsion of the reactive mixture is cooled, and it was mostly to the respective ambient temperature, for example 10 to 30 0 C.
- the reactive size agents used are preferably alkylketene dimers.
- the mean diameter of the emulsified particles of the reactive sizing agent is less than 500 nm, preferably at most 300 nm, and is usually in the range from 30 to 300 nm, in particular from 40 to 200 nm.
- the particle sizes of the emulsified reactive sizing agents indicated here are weight-average particle sizes. as they can be determined by dynamic light scattering. Methods for this purpose are familiar to the person skilled in the art, for example from H. Wiese in D. Distler, Aqueous Polymer Dispersions, Wiley-VCH 1999, Chapter 4.2.1, p 40ff and literature cited therein and H. Auweter, D. Horn, J. Colloid Interf , Be. 105 (1985) 399, D. Lie, D.
- the reactive sizing agent In order to obtain the most stable dispersion or emulsion of the reactive sizing agent, it is preferably emulsified in the presence of at least one surfactant as a dispersion stabilizer. In most cases, at least one surfactant is first dissolved in water and then the molten reactive sizing agent is first added. However, it is also possible to add the surfactant only during emulsification or afterwards. The addition of the surfactant can be carried out continuously, in stages or at once. This gives a dispersion which z. B. 0.01 to 20 wt .-%, preferably 0.1 to 10 wt .-% and usually 0.2 to 5 wt .-% of at least one surfactant.
- the content of reactive sizing agent in the aqueous dispersion may be, for example, 1 to 60% by weight, preferably 10 to 50% by weight. It is usually in the range of 15 to 30% by weight.
- the surfactants which are suitable as dispersion stabilizers may be, for example, cationic, anionic, amphoteric or nonionic. It is possible to use a surfactant from a single group of said surfactants or mixtures of surfactants which are compatible with each other, i. which are stable next to each other in an aqueous medium and do not form precipitates, for example mixtures of at least one nonionic and at least one anionic surfactant, mixtures of at least one nonionic and at least one cationic surfactant, mixtures of at least two cationic surfactants, mixtures of at least two anionic surfactants or mixtures of at least two nonionic surfactants.
- a dispersion stabilizer in addition to a surfactant, a protective colloid and / or a dispersant can additionally be used.
- a surfactant in addition to a surfactant, a protective colloid and / or a dispersant can additionally be used.
- a protective colloid and / or a dispersant can additionally be used.
- mixtures of at least one surfactant and at least one dispersant or mixtures of at least one surfactant, at least one dispersant and at least one protective colloid are suitable.
- Suitable surfactants are, for example, all surfactants.
- nonionic surfactants are ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C3-C12) and also ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80, alkyl radical: C8-C36).
- suitable nonionic surfactants include the brands Lutensol ® from BASF AG or the Triton ® brands from Union Carbide.
- Particularly preferred are ethoxylated linear fatty alcohols of the general formula
- x are integers in the range of 10 to 24, preferably in the range of 12 to 20.
- the variable y preferably stands for integers in the range of 5 to 50, more preferably 8 to 40.
- Ethoxylated linear fatty alcohols are usually as Mixture of different ethoxylated fatty alcohols with different degree of ethoxylation ago.
- the variable y in the context of the present invention stands for the mean value (number average).
- Suitable nonionic surface-active substances are also copolymers, in particular block copolymers of ethylene oxide and at least one C 3 -C 10 -alkylene oxide, for example triblock copolymers of the formula
- A is a radical derived from an aliphatic, cycloaliphatic or aromatic diol, e.g. for ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, cyclohexane-1, 4-diyl, cyclohexane-1, 2-diyl or bis (cylohexyl) methane-4 , 4'-diyl, B and B 'independently of one another propan-1, 2-diyl, butane-1, 2-diyl or Phe- nylethanyl y2 and y3 independently represent a number from 2 to 100, y1 and y4 independently from each other represent a number from 2 to 100, wherein the sum y1 + y2 + y3 + y4 is preferably in the range of 20 to 400, which corresponds to a number average molecular weight in the range of 1000 to
- Suitable surface-active substances besides the nonionic surfactants are anionic and cationic surfactants. They can be used alone or as a mixture. The prerequisite for this, however, is that they are compatible with each other. This requirement applies, for example, to mixtures of one compound class in each case and to mixtures of nonionic and anionic surfactants and mixtures of nonionic and cationic surfactants.
- suitable anionic surfactants are sodium lauryl sulfate, sodium dodecyl sulfate, sodium hexadecyl sulfate and sodium dioctyl sulfosuccinate.
- cationic surfactants are quaternary alkylammonium salts, alkylbenzylammonium salts, such as dimethyl-C 2 - to cis-alkylbenzylammonium chlorides, primary, secondary and tertiary fatty amine salts, quaternary amidoamine compounds, alkylpyridinium salts, alkylimidazolinium salts and alkyloxazolinium salts.
- anionic surfactants such as. B. with sulfuric acid esterified (optionally alkoxylated) alcohols, which are usually used in neutralized with alkali lye form.
- Further customary emulsifiers are, for example, sodium alkyl sulfonates, sodium alkyl sulfates, such as, for example, sodium.
- sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sulfosuccinic can be used as anionic emulsifiers and esters of phosphoric acid or phosphorous acid and aliphatic or aromatic see carboxylic acids can be used.
- the component (a) of the paper size mixtures is preferably obtainable by emulsifying a reactive sizing agent in the presence of a surfactant and at least one dispersant and / or at least one protective colloid.
- dispersants are, for example, condensates of naphthalenesulfonic acid and formaldehyde, condensates of a salt of naphthalenesulfonic acid or ligninsulfonic acid or salts thereof.
- Suitable salts of naphthalenesulfonic acid and lignosulfonic acid are preferably the products completely or partially neutralized with sodium hydroxide solution, potassium hydroxide solution, ammonia or calcium hydroxide.
- amphiphilic polymers or nanoparticles of water-insoluble organic polymers or of water-insoluble inorganic compounds can also be used as dispersants.
- Stabilizers of this type are, for example, nanoscale silica and nanoscale alumina.
- the component (a) of the mixtures according to the invention is therefore obtainable by emulsifying a reactive sizing agent in the presence of a surfactant and at least one dispersant selected from the group consisting of condensates of naphthalenesulfonic acid and / or salts and formaldehyde, lignosulfonic acid or its salts, amphiphilic polymers and / or nanoparticles organic polymers or inorganic compounds.
- amphiphilic polymers used as dispersants may have an average molecular weight Mw of, for example, 1000 to 100,000. They are used in combination with a surfactant as a dispersion stabilizer. Examples of amphiphilic polymers are copolymers comprising units of
- hydrophobic monoethylenically unsaturated monomers and (ii) monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated sulfonic acids, monoethylenically unsaturated phosphonic acids or mixtures thereof and / or basic monomers
- Suitable hydrophobic monoethylenically unsaturated monomers for preparing the amphiphilic polymers are, for example
- styrene methylstyrene, ethylstyrene, acrylonitrile, methacrylonitrile, C 2 to C 6 olefins, esters of monoethylenically unsaturated C 3 to C 8 carboxylic acids and monohydric alcohols, vinyl alkyl ethers, vinyl esters or mixtures thereof.
- Isobutene, diisobutene is preferably used from this group of monomers.
- Styrene and acrylic acid esters such as ethyl acrylate, isopropyl acrylate, n-butyl acrylate and sec-butyl acrylate.
- the amphiphilic copolymers are preferably contained as hydrophilic monomers
- the acidic monomers may be in the form of the free acids or in partially or completely neutralized form.
- hydrophilic monomers are basic monomers. They may be polymerized with the hydrophobic monomers (i) alone or in admixture with the above acidic monomers. When mixtures of basic and acidic monomers are used, amphoteric copolymers are formed, which are anionically or cationically charged, depending on the molar ratio of the copolymerized acidic to basic monomers.
- Basic monomers are, for example, di-C 1 to C 2 -alkylamino-C 2 to C 4 -alkyl (meth) acrylates or diallyldimethylammonium chloride.
- the basic monomers may be in the form of the free bases, the salts with organic or inorganic acids or in the form quaternized with alkyl halides.
- the salt formation or the quaternization, at which the basic monomers become cationic, can be partial or complete.
- Examples of such compounds are dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, diethylaminopropyl methacrylate, diethylaminopropyl acrylate and / or dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and / or diallyldimethylammonium chloride.
- amphiphilic copolymers in the form of the free acid are not sufficiently soluble in water, they are used in the form of water-soluble salts, for. B. using the corresponding alkali metal, alkaline earth metal and ammonium salts.
- These salts are prepared, for example, by partial or complete neutralization of the free acid groups of the amphiphilic copolymers with bases, e.g. For example, sodium hydroxide solution, potassium hydroxide solution, magnesium oxide, ammonia or amines such as triethanolamine, ethanolamine, morpholine, triethylamine or butylamine are used for neutralization.
- bases e.g.
- bases e.g.
- the acid groups of the amphiphilic copolymers are neutralized with ammonia or sodium hydroxide solution.
- the water solubility of basic monomers or of copolymers which contain such monomers in copolymerized form can be increased by partial or complete neutralization with a mineral acid such as hydrochloric acid or sulfuric acid or by addition of an organic acid such as acetic acid or p-toluenesulfonic acid.
- a mineral acid such as hydrochloric acid or sulfuric acid
- an organic acid such as acetic acid or p-toluenesulfonic acid.
- the acid numbers of the amphiphilic copolymers are, for example, 50 to 500, preferably 150 to 350 mg KOH / g of polymer.
- copolymers may optionally contain, as further monomers (iii), units of maleic monoesters in copolymerized form.
- Such copolymers are obtainable, for example, by copolymerizing copolymers of styrene, diisobutene or isobutene or mixtures thereof with maleic anhydride in the absence of water and reacting the copolymers with alcohols after the polymerization, with from 5 to 50 per mole of anhydride groups in the copolymer Mol% of a monohydric alcohol.
- Suitable alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
- polyhydric alcohols such as glycol or glycerol.
- the reaction is carried out only to the extent that only one OH group of the polyhydric alcohol reacts with the anhydride group. If the anhydride groups of the copolymers are not completely reacted with alcohols, the ring opening of the anhydride groups not reacted with alcohols is effected by addition of water.
- Suitable dispersion stabilizers are mixtures of at least one surfactant and, for example, commercially available polymers of monoethylenically unsaturated acids and also graft polymers of N-vinylformamide on polyalkylene glycols, which are described, for example, in WO 96/34903.
- the grafted vinylformamide units may optionally be hydrolyzed to form vinylamine units.
- the proportion of grafted vinylformamide units is preferably 20 to 40 wt .-%, based on polyalkylene glycol. Polyethylene glycols having molecular weights of 2,000 to 10,000 are preferably used.
- Suitable dispersion stabilizers are mixtures of at least one surfactant and zwitterionic polyalkylenepolyamines and / or zwitterionic polyethyleneimines.
- Such compounds are known for example from EP-B 0 1 12 592. They are obtainable, for example, by first alkoxylating a polyalkylene polyamine or polyethyleneimine, eg. For example, with ethylene oxide, propylene oxide and / or butylene oxide and the alkoxylation subsequently quaternized, eg with methyl bromide or dimethyl sulfate and the quaternized, alkoxylated products then sulfated with chlorosulfonic acid or sulfur trioxide.
- the molar mass of the zwitterionic polyalkylenepolyamines is, for example, 1000 to 9000, preferably 1500 to 7500.
- the zwitterionic polyethyleneimines preferably have molecular weights in the range from 1500 to 7500 daltons.
- Component (a) of the paper size mixtures is also advantageously obtainable by emulsifying a reactive sizing agent in the presence of a surfactant and at least one protective colloid, which is for example selected from
- the protective colloids generally have average molecular weights M w of above 500, preferably of more than 1000 to at most 100 000, usually up to 60 000.
- water-soluble cellulose derivatives such as carboxymethylcellulose and graft polymers of vinyl acetate and / or Vinyl propionate on polyethylene glycols and / or polysaccharides into consideration.
- Water-soluble starches, starch derivatives and proteins are described, for example, in Römpp, Chemie Lexikon 9th Edition, Volume 5, page 3569 or in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/2, Chapter IV Conversion of Cellulose and Starch of E. Husemann and R. Werner, pages 862-915 and in Ullmann's Encyclopedia for Industrial Chemistry, 6th edition, volume 28, pages 533 ff under polysaccharides.
- Suitable protective colloids are in particular all types of water-soluble starch, for.
- water-soluble starch for.
- amylose and amylopectin native starches, hydrophobically or hydrophilically modified starches, anionic starches, cationically modified starches, maltodextri- ne, degraded starches, wherein the starch degradation can be carried out, for example, oxidatively, thermally, hydrolytically or enzymatically and wherein for the starch degradation both native and modified starches can be used.
- Other suitable protective colloids are dextrins and crosslinked water-soluble starches which are water-swellable.
- the molecular weight degradation is preferably carried out enzymatically.
- the average molecular weight M w of the degraded starches is, for example, 500 to 100,000, preferably 1,000 to 30,000.
- the degraded starches have, for example, an intrinsic viscosity [ ⁇ ] of 0.04 to 0.5 dl / g.
- Such starches are described, for example, in EP-B 0 257 412 and in EP-B 0 276 770.
- protective colloids are used in the polymerization, the amounts used are, for example, from 0.5 to 50, in particular from 5 to 40, preferably from 10 to 30,% by weight, based on the monomers used in the polymerization.
- Particularly preferred dispersion stabilizers are combinations of at least one surfactant and at least one degraded native starch or at least one water-soluble cationic starch and mixtures of at least one surfactant and a dispersant of a condensate of naphthalenesulfonic acid and formaldehyde.
- the condensates of naphthalenesulfonic acid and formaldehyde may optionally be modified by condensing urea.
- the condensates can be used in the form of the free acids as well as in partially or completely neutralized form.
- Suitable neutralizing agents are preferably sodium hydroxide solution, potassium hydroxide solution, ammonia, sodium bicarbonate, sodium carbonate or potassium carbonate.
- Lignosulfonic acid or its salts are also suitable as dispersants.
- calcium hydroxide or calcium oxide is also suitable for the partial or complete neutralization of lignin sulfonic acid.
- the component (a) of the mixtures according to the invention is preferably obtainable by emulsifying a reactive sizing agent in the presence of an anionic surfactant and at least one dispersant of a condensate of naphthalenesulfonic acid and formaldehyde and optionally at least one protective colloid.
- the aqueous dispersions of a reactive sizing agent described above are stable. They are mixed with at least one aqueous dispersion of an emulsion polymer of at least one ethylenically unsaturated monomer (component (b) of the mixtures according to the invention) to prepare the paper size compositions of the invention.
- the mixing of the dispersions can be carried out, for example, in a container in which, for example, component (a) is introduced into the mixture (dispersion of a reactive sizing agent) and the aqueous dispersion of an emulsion polymer (component (b)) is metered in with stirring.
- Component (b) can be added continuously, stepwise or all at once to the original.
- the mixtures according to the invention are also obtainable if the component (b) is initially introduced in a container and the component (a) is metered into the original continuously, in stages or at once. Likewise it is possible both To combine components continuously with the help of a two-fluid nozzle or a static mixer.
- the temperature can fluctuate during the mixing process in a wide range. It is, for example, at 10 to 95, usually at 15 to 60 0 C.
- the mixing of the two components (a) and (b) takes place at the respective room temperature.
- An aqueous dispersion is obtained in which the dispersed constituents of components (a) and (b) are present separately next to one another.
- the weight ratio of components (a) and (b) in the mixtures according to the invention is in particular 5: 1 to 1: 5.
- these dispersions are an anionic or cationic charge or are not charged.
- the pH of the aqueous dispersions of the reactive sizes is, for example, 2 to 7, preferably 3 to 5.
- Aqueous dispersions of emulsion polymers of at least one ethylenically unsaturated monomer (component (b) of the mixtures according to the invention) are known. They are prepared by polymerizing the monomers in an aqueous medium in the presence of surfactants and radical-forming polymerization initiators.
- Suitable emulsion polymers are, for example, polymers comprising at least 40% by weight of so-called main monomers selected from C 1 - to C 20 -alkyl (meth) acrylates, vinyl esters of saturated carboxylic acids containing up to 20 C atoms, vinylaromatics having bis to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers containing from 1 to 10 C-atoms alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers are built up.
- main monomers selected from C 1 - to C 20 -alkyl (meth) acrylates, vinyl esters of saturated carboxylic acids containing up to 20 C atoms, vinylaromatics having bis to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers containing from 1 to 10 C-atoms alcohols, ali
- the emulsion polymers are preferably a polymer which consists of at least 70% by weight, particularly preferably at least 95% by weight, of so-called main monomers which are emulsifiable in water.
- Suitable monomers of this type are also vinyl and allyl esters of saturated aliphatic car- carboxylic acids having 1 to 18 carbon atoms, for example vinyl acetate, vinyl propionate and the vinyl esters of Versatic® acids (vinyl versatates), vinyl halides such as vinyl chloride and vinylidene chloride and C 2 -C 6 -olefins such as ethylene, propene, 1-butene and n-hexene.
- Preferred monomers are vinylaromatic monomers, C 2 -C 18 -alkyl acrylates, in particular C 2 -C 8 -alkyl acrylates, especially tert-butyl acrylate, and C 2 -C 18 -alkyl methacrylates and in particular C 2 -C 4 -alkyl methacrylates.
- At least 60% by weight of the main monomers used in the emulsion polymerization are selected from vinylaromatic monomers, in particular styrene, esters of methacrylic acid with C 2 -C 4 alkanols and tert-butyl acrylate.
- Particularly preferred monomers of this type are vinyl aromatic monomers, especially styrene, and mixtures of vinyl aromatic monomers with the above-mentioned C2-C8 alkyl acrylates and / or C2-C4 alkyl methacrylates.
- the monomer composition may further contain up to 20% by weight, based on the total weight of the monomers, of one or more monoethylenically unsaturated monomers (v) other than the main monomers (iv).
- the proportion of monomers (v) in the total amount of monomers is preferably 15% by weight, in particular up to 5% by weight.
- the monomers (v) are used only in amounts such that the resulting polymers are insoluble in water, so that one always receives dispersions.
- the monomers (v) include in particular monoethylenically unsaturated monomers which have at least one acid group such as a sulfonic acid, a phosphonic acid or one or two carboxyl groups and the salts of these monomers, in particular the alkali metal salts, for.
- the alkali metal salts for.
- sodium or potassium salts and ammonium salts as the sodium or potassium salts and ammonium salts.
- This group of monomers (v) includes ethylenically unsaturated sulfonic acids, in particular vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloxyethanesulfonic acid, 2-methacryloxyethanesulfonic acid, 3-acryloxy- and 3-methacryloxypropanesulfonic acid, vinylbenzenesulfonic acid and salts thereof, ethylenically unsaturated Phosphonic acids, such as vinylphosphonic acid and vinylphosphonic and methyl esters and their salts and ⁇ , ß-ethylenically unsaturated C3-Cs mono- and C 4 -Cs dicarboxylic acids, in particular acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
- ethylenically unsaturated sulfonic acids in particular vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic
- the proportion of acid group-containing monomers is often not more than 20 wt .-%, preferably not more than 15 wt .-%, z. B. 0.1 to 15 wt .-% and in particular 0.5 to 10 wt .-%, based on the total amount of the monomers constitute.
- the monomers of group (v) also include monoethylenically unsaturated, neutral monomers such as the amides of the abovementioned ethylenically unsaturated carboxylic acids, in particular acrylamide and methacrylamide, hydroxyalkyl esters of the aforementioned ⁇ , ⁇ -ethylenically unsaturated Cs-Cs monocarboxylic acids and the C 4 -Cs Dicarboxylic acids, in particular 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, 2- and 3-hydroxypropyl methacrylate, esters of the abovementioned monoethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 4 -polyalkylene glycols, in particular the esters of these carboxylic acids with polyethylene glycol or alkyl-polyethylene glycols, wherein the (alkyl) polyethylene glycol radical usually has a mo
- the monomers (v) also include N-vinylamides such as N-vinylformamide, N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam.
- the proportion of these monomers is also chosen so that the resulting polymers are insoluble in water. It is preferably not more than 20 wt .-%, and in particular not more than 10 wt .-%, z. B. 0.1 to 10 and in particular 0.5 to 5 wt .-%, based on the total amount of the monomers.
- Monomers of group (v) furthermore include monoethylenically unsaturated monomers which have at least one cationic group and / or at least one amino group which can be protonated in the aqueous medium, a quaternary ammonium group, a protonatable imino group or a quaternized imino group.
- monomers having a protonatable imino group are N-vinylimidazole and N-vinylpyridines.
- monomers having a quaternized imino group are N-alkylvinylpyridinium salts and N-alkyl-N'-vinylimidazolinium salts such as
- R 1 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl
- R 2 , R 3 independently of one another Ci-C 4 -AlkVl, in particular methyl
- R 4 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl
- A is C 2 -C 8 alkylene, e.g. B. 1, 2-ethanediyl, 1, 2- or 1, 3-propanediyl, 1, 4-butanediyl or 2-methyl-1, 2-propanediyl, which is optionally interrupted by 1, 2 or 3 non-adjacent oxygen atoms is and X- for an anion equivalent, e.g. B. for Ch, HSO 4 -, ⁇ A SO 4 2 " or CH 3 OSO 3 - etc.,
- Examples of such monomers are 2- (N, N-dimethylamino) ethyl acrylate,
- the proportion of cationic monomers in the emulsion polymer is advantageously 0.1 to 20 wt .-%, in particular 0.5 to 10 wt .-%, and particularly preferably 1 to 7 wt .-%, based on the total amount of the monomers.
- the polymers may optionally contain a further group of monomers (vi) polymerized, which can usually be used as a crosslinker in an emulsion polymerization.
- the proportion of monomers (vi) having two or more ethylenically unsaturated double bonds usually makes no more than 10 wt .-%, usually not more than 5 wt .-%, in particular not more than 2 wt .-%, z , B. 0.01 to 2 wt .-% and in particular 0.05 to 1, 5 wt .-%, based on the total amount of the monomers.
- crosslinkers are butanedioldiacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, glycol dicarylate, glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, diacrylates and dimethacrylates of alkoxylated dihydric alcohols, divinylurea and / or conjugated diolefins such as butadiene or isoprene.
- a reactive functional group for example an oxirane group, a reactive carbonyl group, eg. An acetoacetato group, an isocyanate group, an N-hydroxymethyl group, an N-alkoxymethyl group, a trialkylsilyl group, a trialkoxysilyl group or other nucleophile-reactive group.
- emulsion polymers whose Monomerzusammen- reduction is selected so that the resulting polymer has a glass transition temperature of at least 0, preferably at least 10 0 C, in particular in the range of 20 to 130 0 C, respectively.
- the monomers (i) are selected in the monomer mixture so that they correspond to a polymer 1 having a theoretical glass transition temperature according to Fox T g (Fox) of at least 50 0 C.
- Fox TG Fox, Bull. Am. Phys Soc. (Ser. II) 1, 123 [1956] and Ullmann's Encyclopedia of Industrial Chemistry, Weinheim (1980), pp 17-18
- Fox TG Fox, Bull. Am. Phys Soc. (Ser. II) 1, 123 [1956] and Ullmann's Encyclopedia of Industrial Chemistry, Weinheim (1980), pp 17-18
- X 1 , X 2 , ..., X n is the mass fractions of the monomers 1, 2, ..., n and T 9 1 , T 9 2 , ..., T 9 "the glass transition temperatures of each of only one of Monomers 1, 2, ..., n of polymers constructed in degrees Kelvin .
- the latter are, for example, from Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p 169 or from J. Brandrup, EH Immergut, Polymer Handbook 3rd ed., J. Wiley, New York 1989.
- the polymerization of the monomers is carried out by the method of emulsion polymerization, i. the monomers to be polymerized are present in the polymerization mixture as an aqueous emulsion.
- the monomers to be polymerized are present in the polymerization mixture as an aqueous emulsion.
- a dispersion stabilizer for the preparation of the aqueous dispersions of reactive sizes, e.g.
- surfactants in particular anionic surfactants, water-soluble starch, preferably anionic starch and protective colloids.
- the monomers may be initially charged in the reactor prior to the start of the polymerization or added under polymerization conditions in one or more portions or continuously to the polymerizing reaction mixture. For example, you can submit the majority of the monomers, in particular at least 80% and particularly preferably the total amount in the polymerization vessel and then immediately start the polymerization by adding a polymerization initiator.
- a further process variant consists in initially introducing a part (for example 5 to 25%) of the monomers or the monomer emulsion in the polymerization reactor, starting the polymerization by adding an initiator and the remaining amount of monomers or monomer emulsion to the reactor feeds continuously or in portions and completes the polymerization of the monomers.
- the polymerisate Onsinitiator can be presented in this process variant, for example, partially or completely in the reactor or metered separately from the remaining monomers in the reactor.
- the starters which are suitable for emulsion polymerization are, in principle, all polymerization initiators which are suitable and usually used for emulsion polymerization and which initiate free-radical polymerization of ethylenically unsaturated monomers.
- polymerization initiators which are suitable and usually used for emulsion polymerization and which initiate free-radical polymerization of ethylenically unsaturated monomers.
- azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide, 1, 1 '.
- the polymerization is preferably carried out using a redox initiator system, in particular a redox initiator system which contains as oxidizing agent a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide.
- a redox initiator system which contains as oxidizing agent a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide.
- the redox initiator systems preferably contain a sulfur compound, which is especially selected from sodium hydrogen sulfite, sodium hydroxymethanesulfinate and the bisulfite adduct of acetone.
- sulfur compound which is especially selected from sodium hydrogen sulfite, sodium hydroxymethanesulfinate and the bisulfite adduct of acetone.
- suitable reducing agents are phosphorus-containing compounds such as phosphorous acid, hypophosphites and pho
- redox initiator systems may contain an addition of small amounts of redox metal salts, such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.
- redox metal salts such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.
- Particularly preferred redox initiator systems are acetone bisulfite adduct / organic hydroperoxide such as tert-butyl hydroperoxide; Sodium disulfite (Na2S2 ⁇ s) / organic hydroperoxide such as tert-butyl hydroperoxide; Sodium hydroxymethanesulfinate / organic hydroperoxide such as tert-butyl hydroperoxide; and ascorbic acid / hydrogen peroxide.
- the initiator is usually employed in an amount of 0.02 to 2% by weight and in particular 0.05 to 1.5% by weight, based on the amount of the monomers.
- the optimum amount of initiator naturally depends on the initiator system used and can be determined by the person skilled in the art in routine experiments.
- the initiator may be partially or completely charged in the reaction vessel. Usually a part the amount of initiator together with a part of the monomer emulsion and the remaining initiator continuously or batchwise together with the monomers, but separately, added.
- Pressure and temperature are of minor importance for carrying out the polymerization of the monomers.
- the temperature naturally depends on the initiator system used.
- the optimum polymerization temperature can be determined by a person skilled in the art with the aid of routine experiments.
- the polymerization temperature is in the range of 0 to 110 0 C, often in the range of 30 to 95 0 C.
- the polymerization is usually carried out at atmospheric pressure or ambient pressure. But it can also at elevated pressure, z. B. to 10 bar or at reduced pressure z. B. at 20 to 900 mbar, but usually be carried out at> 800 mbar.
- a dispersion stabilizer is added to stabilize the resulting emulsion polymers, it is preferable to add at least one further surface-active substance in an amount of, for example, up to 5% by weight, e.g. B. 0.1 to 5 wt .-%, based on the monomer to be polymerized monomers.
- a further surface-active substances in addition to the nonionic surface-active substances in particular also anionic emulsifiers, z.
- alkyl sulfates As alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alkyl ether sulfates, alkylaryl ether sulfates, anionic starch, sulfosuccinates such as sulfosuccinic monoesters and sulfosuccinic and alkyl ether and further cationic E- emulsifiers into consideration. These compounds are used as surfactants in the preparation of the component (a) of the mixtures according to the invention.
- the emulsion polymerization of the monomers is carried out in the presence of, for example, up to 20% by weight, usually up to 10% by weight, based on the total dispersion, of a cationically or anionically modified starch.
- a cationically or anionically modified starch emulsion polymerization of the monomers
- the emulsion polymerization can optionally be carried out in the presence of at least one polymerization regulator.
- polymerization regulators are organic compounds which contain sulfur in bound form, such as dodecylmercaptan, thiodiglycol, ethylthioethanol, di-n-butylsulfide, di-n-octylsulfide, diphenyl sulfide, diisopropyl disulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, 3 Mercaptopropan-1, 2-diol, 1, 4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioacetic acid and thiourea, aldehydes such as formaldehyde, acetaldehyde and propionaldehyde, organic acids such as formic acid, sodium formate or ammonium format
- the amount used in each case for example, 0.01 to 5, preferably 0.1 to 1 wt .-%, based on the monomers used in the polymerization.
- Polymerization regulators and crosslinkers can be used together in the polymerization. This can be used, for example, to control the rheology of the resulting polymer dispersions.
- the polymerization is generally carried out at pH values of 2 to 9, preferably in the weakly acidic range at pH values of 3 to 5.5.
- the pH can be adjusted to the desired value before or during the polymerization with customary acids such as hydrochloric acid, sulfuric acid or acetic acid or else with bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia, ammonium carbonate, etc.
- the dispersion is preferably adjusted to a pH of between 5 and 7 using sodium hydroxide solution, potassium hydroxide solution or ammonia.
- a postpolymerization is expediently carried out after completion of the actual polymerization.
- the polymer dispersion after completion of the main polymerization for example, an initiator from the group of hydrogen peroxide, peroxides, hydroperoxides and / or azo starters.
- suitable reducing agents such as ascorbic acid or sodium bisulfite
- oil-soluble, sparingly soluble in water initiators are used, for.
- the reaction mixture is heated, for example, to a temperature which corresponds to the temperature at which the main polymerization has been carried out or which may be up to 20 ° C., preferably se is up to 10 0 C higher.
- the main polymerization is complete when the polymerization initiator is consumed or the monomer conversion is, for example, at least 98%, preferably at least 99.5%.
- tert-butyl hydroperoxide is preferably used.
- the polymerization is carried out for example in a temperature range of 40 to 100 0 C, usually 50 to 95 ° C.
- a complexing agent for heavy metal ions can be added to the polymer dispersion in an amount such that all heavy metal ions are complexed.
- the starch-containing polymer dispersions contain dispersed particles having an average particle size of, for example, 20 to 500 nm, preferably 50 to 250 nm.
- the mean particle size can be determined by methods known to the person skilled in the art, such as, for example, laser correlation spectroscopy, ultracentrifugation or CHDF (Capillary Hydodynamic Fractionation). Another measure of the particle size of the dispersed polymer particles is the LD (translucency) value.
- the particular polymer dispersion to be examined is measured in 0.1% by weight aqueous dilution in a cuvette with an edge length of 2.5 cm with light of wavelength 600 nm and with the appropriate permeability of water under the same measurement conditions compared.
- the permeability of water is given as 100%.
- the finer the dispersion the higher the LD value measured by the method described above.
- the average particle size can be calculated from the measured values, cf. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prague, 1976, Edice Marco, Rada D-DATA, SVAZEK D-1.
- the solids content of the starch-containing polymer dispersion is, for example, 5 to 50% by weight, and is preferably in the range of 15 to 40% by weight.
- the paper size mixtures according to the invention comprise, for example, as component (b) an emulsion polymer
- Atoms having saturated carboxylic acids vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitrile, vinyl halide, vinyl ethers of 1 to 10
- component (v) optionally at least one cationic and / or at least one anionic monomer.
- component (b) consists of an emulsion polymer
- Component (b) used in a particularly preferred embodiment is an aqueous dispersion of an emulsion polymer obtainable by polymerizing ethylenically unsaturated monomers in the presence of a degraded starch.
- emulsion polymers are also known. They are used, for example, as a sizing agent for paper, cf. JP-A 58/1 15 196, EP-B 0 257 412, EP-B 0 267 770, EP-A 0 307 812, EP-A 0 536 597, EP-A 1 056 783, WO 00/23479, WO 02/14393, EP-B 1 165 642 and WO 2004/078807.
- Suitable starches are all native starches such as potato starch, corn starch, wheat starch, rice starch, starches with an amylopectin content of more than 95% and tapioca starch and cationically and anionically modified starches.
- the starches are subjected to molecular weight degradation before polymerization is carried out in the solution of degraded starch.
- the breakdown of the starch can be carried out oxidatively, hydrolytically or enzymatically.
- the starch is enzymatically degraded.
- the molecular weights M w of the degraded starches are, for example, in the range from 1000 to 100 000, preferably from 1000 to 60 000.
- the polymer dispersions may contain, for example, up to 20% by weight of at least one degraded starch. In most cases, the content of degraded starch in the emulsion polymers used as component (b) is 5 to 15% by weight.
- aqueous dispersions obtainable by free-radical polymerization of monomers of the abovementioned groups (iv) and (v) in the presence of low molecular weight prepolymers as emulsifier. Such prepolymers are known, for example, from EP-A 0 051 144.
- ком ⁇ онентs are prepared by a two-stage polymerization, wherein in the first polymerization stage, a monomer mixture containing from 2.5 to 10 moles of at least one nonionic, hydrophobic, ethylenic, per mole of a nitrogen-containing monomer carrying an amino and / or quaternary ammonium group unsaturated monomers, 0.5 to 1, 5 moles of an ethylenically unsaturated carboxylic acid and optionally up to 9 moles of a nonionic, hydrophilic, ethylenically unsaturated monomer polymerized in a water-miscible solvent in the manner of a solution copolymerization, then the solution of the prepolymer with water diluted and polymerized therein ethylenically unsaturated monomers in the manner of emulsion polymerization.
- Suitable solvents for the preparation of the prepolymers are, for example, carboxylic acids such as formic acid, acetic acid and propionic acid, alcohols such as methanol, ethanol, n-propanol or isopropanol and ketones such as acetone or methyl ethyl ketone and also dimethylformamide.
- carboxylic acids such as formic acid, acetic acid and propionic acid
- alcohols such as methanol, ethanol, n-propanol or isopropanol
- ketones such as acetone or methyl ethyl ketone and also dimethylformamide.
- the above-described monomers (iv) and (v) and optionally (vi) may be polymerized in an aqueous solution of such a prepolymer in the manner of emulsion polymerization.
- the paper size mixtures according to the invention can, for. Example, as component (b) an aqueous dispersions of an emulsion polymer containing by radical polymerization of
- Atoms having saturated carboxylic acids vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitrile, vinyl halide, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbon having 2 to 8
- a further example of polymers which are suitable as component (b) of the mixtures according to the invention are emulsion polymers obtainable by free-radical polymerization of (iv) from 30 to 60% by weight of at least one optionally substituted styrene, acrylonitrile and / or methacrylonitrile (v) from 5 to 50% by weight of at least one acrylic acid C 1 -C 4 -alkyl ester and / or of a methacrylic acid C 1 -C 4 (iii) from 5 to 30% by weight of at least one C 4 to C 24 olefin,
- the paper size mixtures may also contain as component (b) at least one non-dispersible water-soluble or water-dispersible polymer from the group of polymers containing ethyleneimine units, water-soluble polyurethanes, water-soluble polyesters, water-soluble ethylene copolymers with anionic and / or cationic monomers or containing their mixtures.
- the molecular weights M w of these polymers are for example at least 5,000, preferably at least 100,000. They are usually in the range from 50,000 to 500,000.
- Ethylenimine units containing polymers are known. They are, for example, by polymerizing ethyleneimine in an aqueous medium in the presence of z. As acids, halogenated hydrocarbons or Lewis acids as a catalyst. They are also accessible by grafting of ethyleneimine compounds containing basic nitrogen atoms, for. B. by grafting condensates of a polyamidoamine and a dicarboxylic acid with ethyleneimine, cf. DE-B 24 34 816. A commercially available product of this kind is Polymin® SK from BASF, Ludwigshafen.
- Vinylamine-containing polymers are obtainable by hydrolysis of vinylformamide units containing polymers.
- Polyvinylamines are prepared, for example, by hydrolysis of homopolymers of N-vinylformamide, the degree of hydrolysis being, for example, up to 100%, usually 70 to 95%.
- High molecular weight copolymers of N-vinylformamide with other ethylenically unsaturated monomers such as vinyl acetate, vinyl propionate, methyl acrylate, Methacrylklaremethy- ester, acrylamide, acrylonitrile and / or methacrylonitrile, can be hydrolyzed to Vinylamineinomme containing polymers and according to the invention as component (b) sets.
- the polymers containing vinylamine units are cationic.
- component (b) of the mixtures according to the invention are non-dispersing, modified polyamines grafted with ethyleneimine and optionally crosslinked, polyetheramides, polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, polyvinyltetrahydropyrines, poly (dialkylaminoalkylvinyl ethers) and also poly (Dialkylaminoalkyl (meth) acrylates) in protonated or in quaternized form.
- the finely divided, aqueous mixtures of (a) a dispersion of a reactive sizing agent described above and (b) an emulsion polymer and / or a non-dispersing water-soluble polymer are used as sizing agents for paper and paper products such as cardboard and paperboard. They can be used both as surface sizing agents and as engine size agents in the customary amounts. Preferably, the application is as a surface sizing agent.
- the novel mixtures of the dispersions of components (a) and (b) can be processed with all process methods suitable for surface sizing.
- the dispersion is usually added to the size press liquor in an amount of 0.05 to 5% by weight, based on solid substance, and depends on the desired degree of sizing of the papers or paper products to be finished.
- the size press fleet may contain other substances such.
- starch pigments, optical brighteners, biocides, solidifiers for paper, fixing agents, defoamers, retention aids, and / or dehydrating agents.
- the sizing agent dispersion can be applied to paper, cardboard or cardboard by means of a size press or other application units such as a film press, Speedsizer or Gateroll.
- the amount of polymer thus applied to the surface of paper products is, for example, 0.005 to 1.0 g / m 2 , preferably 0.01 to 0.5 g / m 2 .
- the paper sizes mixtures according to the invention can be used for the production of all types of paper, for.
- As of writing and printing papers and packaging papers in particular of papers for the packaging of liquids.
- Paper products glued with the fine-particle, starch-containing polymer dispersions according to the invention have, compared with papers which are known with known sizing agents. with improved sizing, good instant sizing, improved ink-jet printability, and good toner adhesion.
- the percentages in the examples always mean percent by weight, the parts are parts by weight.
- the particle sizes were determined using a High Performance Particle Sizer (HPPS) from Malvern using a He-Ne laser (633 nm) at a scattering angle of 173 °.
- HPPS High Performance Particle Sizer
- Sulfonate 120 g stearyidiketene, 871, 3 g of demineralized water, 12 g Natriumdocecylsul- and 7.6 g of a condensation product of naphthalenesulfonic acid and formaldehyde (Tamol ® NNP) were mixed and heated to a temperature of 85 ° C. Once this temperature was reached, the mixture was pre-emulsified with the aid of an Ultraturrax ® apparatus at 6000 rpm over 5 minutes and then at 80 0 C three times with a homogenizer (AVP Gaulin LAB 40, 600 bar) emulsified and rapidly cooled to room temperature. A finely divided aqueous dispersion of stearyl diketene having an average particle size distribution of 144 nm was obtained.
- the determination of the degree of sizing was carried out according to Cobb ⁇ O according to DIN EN 20 535.
- the HST value was determined according to the Hercules Sizing Test in accordance with Tappi Standard T 530.
- the Inkschwimmzeit was carried out according to DIN 53 126 with a Sheffieldprüfinte blue.
- the toner adhesion was carried out with an IGT tester according to the regulation EN 12 283.
- An anionically modified potato starch was dissolved by heating at 95 ° C. for 30 minutes. Subsequently, the starch solution was added to the polymer dispersion to be tested, and diluted with water, so that in the finished mixture, a starch concentration of 8% was present. The mixture of starch solution and the polymer dispersion was then coated by means of a size press on a wood-free, unsized paper with a grammage of 80 g / m 2 at a temperature of 55 0 C. The preparation uptake was in the range of 50-60%. Subsequently, the papers thus treated were dried by means of contact drying at 90 0 C, air-conditioned for 24 h at 50% humidity and then subjected to the tests indicated above.
- aqueous dispersion of sizing agents (Basoplast ® 400DS) based on a styrene / butyl acrylate polymer.
- the solids content of the dispersion was 24.9%, the particle size distribution 101 nm.
- a native corn starch was brought into solution with heating to 95 0 C for 30 minutes and degraded by the addition of alpha-amylase to a viscosity of about 30mPas (Brookfield, spindle 1, 50 0 C).
- the starch solution each with the dispersions to be tested (ie, sizing agent from Examples 1-6 and Comparative Examples 1-5), and diluted with water, so that in the finished mixture, a starch concentration of 8% was present.
- the mixture of starch solution and size dispersion was then applied to a test liner by means of a size press (100% recycled paper, 100 g / m 2) at a temperature of 55 0 C.
- the preparation uptake was in the range of approximately 65%.
- the papers thus treated were dried by means of contact drying at 90 0 C, air-conditioned for 24 h at 50% humidity and then subjected to the tests indicated above. The results are shown in Table 2. (Concentrate sizing agent in the mixture
- Leaves are dried on a steam-heated drying cylinder at a temperature of 90 0 C to a water content of 5%, then stored for 24 hours at 25 0 C and a relative humidity of 50% and then determines the values for Cobb 60 and the ink buoyancy.
- the measured values are given in Table 3. Table 3
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Abstract
Mixtures of paper gluing agents made of a reactive gluing agent dispersed in water and a polymer which are obtainable by mixing: a) an aqueous dispersion of a reactive gluing agent of which the dispersed particles have an average diameter of less than 500 nm, wherein the dispersion is obtainable by emulsification of at least one reactive gluing agent in water in the presence of at least one surfactant; and b) at least one emulsion polymerizate, and/or at least one polymer which is nondispersing relative to reactive gluing agents and which is water soluble, and/or one polymer which is dispersible in water; and use of the above-mentioned mixtures of paper gluing agents for mass gluing and surface gluing of paper and paper products.
Description
Papierleimungsmittelmischungen paper size
Beschreibungdescription
Die Erfindung betrifft Papierleimungsmittelmischungen aus einem in Wasser disper- gierten Reaktivleimungsmittel und einem Polymeren.The invention relates to paper size mixtures of a water-dispersed reactive size and a polymer.
Aus der DE-A 195 12 399 sind Papierleimungsmittelmischungen bekannt, die als erste Komponente eine feinteilige wässrige Dispersion eines Ci4- bis C22-Alkyldiketens und als zweite Komponente eine feinteilige wässrige Polymerdispersion enthalten, die ein Leimungsmittel für Papier ist. Die erste Komponente wird durch Dispergieren von Al- kyldiketenen in Wasser in Gegenwart von kationischer Stärke hergestellt, die einen Amylopektingehalt von mindestens 95 %, vorzugsweise 98 bis 100 % hat. Das Dispergieren der Alkyldiketene kann zusätzlich in Gegenwart von Ligninsulfonsäure, Kondensaten aus Naphthalinsulfonsäure und Formaldehyd, Styrolsulfonsäuregruppen enthaltenden Polymeren oder deren Alkalimetall- und/oder Ammoniumsalzen erfolgen. Der mittlere Teilchendurchmesser der in Wasser dispergierten Alkyldiketene beträgt 0,5 bis 2,5 μm, vorzugsweise 0,8 bis 1 ,5 μm. Gemäß den Angaben in den Beispielen liegt er immer oberhalb von 1 μm. Die Mischungen werden hergestellt, indem man eine Alkyldi- ketendispersion mit einer Polymerdispersion mischt oder dadurch, dass man Alkyldiketene bei einer Temperatur von mindestens 700C in einer Mischung emulgiert, die aus wässrigen Suspensionen von kationischer Stärke mit einem Amylopektingehalt von mindestens 98% und feinteiligen, wässrigen Polymerdispersionen besteht. Solche Mischungen bestehen aus zwei unterschiedlichen Teilchensorten, nämlich aus Teilchen aus Alkyldiketen und Teilchen aus Emulsionspolymer.From DE-A 195 12 399 Papierleimungsmittelmischungen are known which contain as a first component, a finely divided aqueous dispersion of a C 4 - to C22-Alkyldiketens and as a second component, a finely divided aqueous polymer dispersion which is a sizing agent for paper. The first component is prepared by dispersing alkyldiketenes in water in the presence of cationic starch having an amylopectin content of at least 95%, preferably 98 to 100%. The dispersing of the alkyldiketenes can additionally be carried out in the presence of lignosulfonic acid, condensates of naphthalenesulfonic acid and formaldehyde, polymers containing styrenesulfonic acid groups or their alkali metal and / or ammonium salts. The average particle diameter of the water-dispersed alkyldiketenes is 0.5 to 2.5 μm, preferably 0.8 to 1.5 μm. According to the information in the examples, it is always above 1 μm. The mixtures are prepared by ketendispersion an alkyl di- with a polymer dispersion mixed or in that one emulsified alkyldiketenes at a temperature of at least 70 0 C in a mixture, the finely divided aqueous suspensions of cationic starch having an amylopectin content of at least 98%, and , aqueous polymer dispersions. Such mixtures consist of two different types of particles, namely particles of alkyl diketene and particles of emulsion polymer.
Aus der WO 2004/037867 sind Alkyldiketene enthaltende wässrige Polymerdispersionen bekannt, die durch Miniemulsionspolymerisation von hydrophoben monoethyle- nisch ungesättigten Monomeren in Gegenwart von Alkylketendimeren erhältlich sind. Ein einzelnes in Wasser dispergiertes Teilchen enthält sowohl Alkylketendimer als auch hydrophobes Polymerisat. Der mittlere Teilchendurchmesser liegt in dem Bereich von 50 bis 500 nm, vorzugsweise 50 bis 200 nm. Entsprechend aufgebaute Polymerdispersionen, die anstelle von Alkylketendimeren Alkenylbernsteinsäureanhydride enthalten, sind aus der WO 2005/070912 bekannt. Sie werden durch Polymerisieren von hydrophoben Monomeren nach Art einer Miniemulsionspolymerisation in Gegenwart von Alkenylbernsteinsäureanhydriden und gegebenenfalls zusätzlich Alkylketendimeren hergestellt.WO 2004/037867 discloses aqueous polymer dispersions comprising alkyldiketenes which are obtainable by miniemulsion polymerization of hydrophobic monoethylenically unsaturated monomers in the presence of alkylketene dimers. A single particle dispersed in water contains both alkyl ketene dimer and hydrophobic polymer. The average particle diameter is in the range from 50 to 500 nm, preferably 50 to 200 nm. Correspondingly constructed polymer dispersions which contain alkenylsuccinic anhydrides instead of alkylketene dimers are known from WO 2005/070912. They are prepared by polymerizing hydrophobic monomers in the manner of a miniemulsion polymerization in the presence of alkenylsuccinic anhydrides and optionally additionally alkylketene dimers.
Aus der WO 2004/022847 ist die Verwendung von Vinylamineinheiten enthaltenden Polymeren als Promoter für die Masseleimung von Papier bekannt. Darin werden beispielsweise wässrige Dispersionen beschrieben, die Stearyldiketen, kationische Stärke und Polyvinylamin enthalten.
Gegenstand der älteren EP-Anmeldung 06 115 714.5 ist ein Verfahren zur Herstellung von mindestens einen lipophilen Wirkstoff enthaltenden wässrigen Polymerdispersionen durch Emulsionspolymerisation von ethylenisch ungesättigten Monomeren in wässrigem Medium in Gegenwart mindestens eines lipophilen Wirkstoffs, wobei manWO 2004/022847 discloses the use of polymers containing vinylamine units as a promoter for the size sizing of paper. Therein, for example, aqueous dispersions are described which contain stearyl diketene, cationic starch and polyvinylamine. The subject of the earlier EP application 06 115 714.5 is a process for the preparation of at least one lipophilic active substance-containing aqueous polymer dispersions by emulsion polymerization of ethylenically unsaturated monomers in an aqueous medium in the presence of at least one lipophilic active ingredient, wherein
(i) mindestens einen lipophilen Wirkstoff, der eine Wasserlöslichkeit von höchstens 5 g/l (bestimmt bei 25°C und 1013 mbar) und einen Schmelzpunkt unterhalb von 1300C hat, in einer wässrigen Lösung, die mindestens einen Dispersionsstabilisator enthält, unter Bildung einer wässrigen Dispersion des Wirkstoffs mit einer mittleren Teilchengröße von höchstens 1000 nm, vorzugsweise höchstens 500 nm, emulgiert und(I) at least one lipophilic active ingredient having a water solubility of at most 5 g / l (determined at 25 ° C and 1013 mbar) and a melting point below 130 0 C, in an aqueous solution containing at least one dispersion stabilizer, with formation an aqueous dispersion of the active ingredient having an average particle size of at most 1000 nm, preferably at most 500 nm, emulsified and
(ii) eine Monomerzusammensetzung, die mindestens 80 Gew.-% eines neutralen, in Wasser emulgierbaren monoethylenisch ungesättigten Monomeren enthält, in der nach (i) erhaltenen wässrigen Dispersion des Wirkstoffs einer Emulsionspo- lymerisation unterwirft.(ii) subjecting a monomer composition containing at least 80% by weight of a neutral, water-emulsifiable monoethylenically unsaturated monomer to emulsion polymerization in the aqueous dispersion of the active ingredient obtained according to (i).
Als lipophile Wirkstoffe kommen u.a. Alkyldiketene und Alkenylbernsteinsäureanhydri- de in Betracht. Die Teilchen der wässrigen Polymerdispersionen enthalten beispielsweise bei Einsatz von Alkylketendimer als Wirkstoff sowohl Alkylketendimer als auch Emulsionspolymerisat und haben einen mittleren Teilchendurchmesser von höchstens 1000 nm.As lipophilic agents come u.a. Alkyldiketenes and Alkenylbernsteinsäureanhydri- de into consideration. The particles of the aqueous polymer dispersions contain, for example, when using alkyl ketene dimer as the active ingredient both alkyl ketene dimer and emulsion polymer and have an average particle diameter of at most 1000 nm.
Der Erfindung liegt die Aufgabe zugrunde, weitere Produkte für die Papierleimung zur Verfügung zu stellen, die eine möglichst rasche Ausbildung der Leimung bewirken.The invention has for its object to provide other products for paper sizing available, which cause the fastest possible training of sizing.
Die Aufgabe wird erfindungsgemäß gelöst mit Papierleimungsmittelmischungen aus einem in Wasser dispergierten Reaktivleimungsmittel und einem Polymeren, wobei sie erhältlich sind durch Mischen vonThe object is achieved according to the invention with bleach mixtures of a water-dispersed reactive sizing agent and a polymer, wherein they are obtainable by mixing
(a) einer wässrigen Dispersion eines Reaktivleimungsmittels, dessen dispergierte Teilchen einen mittleren Teilchendurchmesser von weniger als 500 nm aufweisen, wobei die Dispersion durch Emulgieren mindestens eines Reaktivleimungsmittels in Wasser in Gegenwart mindestens eines Tensids erhältlich ist, und (b) mindestens eines Emulsionspolymerisates und/oder mindestens eines gegenüber Reaktivleimungsmitteln nicht dispergierend wirkenden, wasserlöslichen Polymers und/oder eines in Wasser dispergierbaren Polymers.(A) an aqueous dispersion of a reactive sizing agent whose dispersed particles have an average particle diameter of less than 500 nm, wherein the dispersion is obtainable by emulsifying at least one reactive sizing agent in water in the presence of at least one surfactant, and (b) at least one emulsion polymer and / or at least one water-soluble polymer which does not disperse reactive wetting agents and / or a water-dispersible polymer.
Besonders bevorzugt sind Papierleimungsmittelmischungen, wobei die Komponente (a) der Mischungen eine wässrige Dispersion eines Reaktivleimungsmittels ist, dessen dispergierte Teilchen einen mittleren Teilchendurchmesser von höchstens 300 nm haben. Die Komponente (a) der Mischungen enthält als Reaktivleimungsmittel eine wäss-
rige Dispersion eines Alkylketendimeren und/oder eines Alkenylbernsteinsäurean- hydrids mit einer mittleren Teilchengröße der dispergierten Teilchen von beispielsweise 30 bis 300 nm.Particularly preferred are paper size mixtures, wherein component (a) of the mixtures is an aqueous dispersion of a reactive sizing agent whose dispersed particles have an average particle diameter of at most 300 nm. Component (a) of the mixtures contains, as a reactive sizing agent, an aqueous aqueous dispersion of an alkyl ketene dimer and / or an alkenyl succinic anhydride having an average particle size of the dispersed particles of, for example, 30 to 300 nm.
Das Gewichtsverhältnis der Komponenten (a) und (b) in der Mischung beträgt beispielsweise 1 : 100 bis 100 : 1 und liegt vorzugsweise in dem Bereich von 1 : 20 bis 20 : 1. Besonders bevorzugt sind Papierleimungsmittelmischungen, die als KomponenteThe weight ratio of components (a) and (b) in the mixture is, for example, 1: 100 to 100: 1 and is preferably in the range from 1:20 to 20: 1. Particularly preferred are paper size mixtures which are used as component
(a) eine wässrige Dispersion eines Alkylketendimeren enthalten, das mit Hilfe eines kationischen, anionischen und/oder nichtionischen Tensids emulgiert ist, und als Komponente(A) an aqueous dispersion of an alkyl ketene dimer emulsified by means of a cationic, anionic and / or nonionic surfactant, and as a component
(b) mindestens ein Emulsionspolymerisat mit einem mittleren Teilchendurchmesser von höchsten 100 nm enthalten.(B) at least one emulsion polymer having a mean particle diameter of 100 nm highest.
Als Alkylketendimere ("AKD") kommen vorzugsweise Ci4- bis C22-Alkyl- oder Alkenyl- diketene in Betracht. Sie werden beispielsweise aus den entsprechenden Carbonsäurechloriden durch Abspaltung von Chlorwasserstoff mit tertiären Aminen hergestellt. Die erfindungsgemäß verwendbaren Ketendimeren können gesättigte oder ungesättig- te, verzweigte oder cyclische Kohlenwasserstoffreste tragen. Beispiele für solche Alkylketendimere sind Tetradecyldiketen, Hexadecyldiketen, Octadecyldiketen, Docosyl- diketen, Palmityldiketen, Oleyldiketen, Stearyldiketen und Behenyldiketen. Vorzugsweise verwendet man Stearyldiketen, Palmityldiketen, Oleyldiketen, Behenyldiketen, Isostearyldiketen oder Mischungen aus Alkyldiketenen z.B. Mischungen aus Behenyl- diketen und Stearyldiketen oder Mischungen aus Stearyldiketen und Palmityldiketen.Suitable alkyl ketene dimers ("AKD") are preferably C 4 - to C 22 -alkyl- or alkenyl-diketenes. They are prepared for example from the corresponding carboxylic acid chlorides by elimination of hydrogen chloride with tertiary amines. The ketene dimers which can be used according to the invention can carry saturated or unsaturated, branched or cyclic hydrocarbon radicals. Examples of such alkyl ketene dimers are tetradecyldiketene, hexadecyldiketene, octadecyldiketene, docosyldiketen, palmityldiketen, oleyldiketen, stearyldiketen and behenyldiketen. Preference is given to stearyl diketene, palmityldiketen, oleyldiketen, Behenyldiketen, Isostearyldiketen or mixtures of Alkyldiketenen eg mixtures of behenyldiketen and Stearyldiketen or mixtures of Stearyldiketen and Palmityldiketen.
Alkenylbernsteinsäureanhydride werden beispielsweise in US 3,102,064, EP-A 0 609 879 und EP-A 0 593 075 ausführlich beschrieben. Sämtliche Alkenylbernsteinsäureanhydride, die bisher in der Literatur als Masseleimungsmittel für Papier beschrieben sind, kommen auch erfindungsgemäß als Wirkstoff in Betracht, entweder allein oder in Kombination mit Alkyldiketenen. Geeignete Alkenylbernsteinsäureanhydride enthalten in der Alkenylgruppe einen Alkylrest mit mindestens 6 C-Atomen, vorzugsweise einen Ci4- bis C24-Olefinrest. Besonders bevorzugte Alkenylbernsteinsäureanhydride enthalten 16 bis 22, meistens 16 bis 18 C-Atome in der Alkenylgruppe. Sie können lineare, zusätzlich ungesättigte oder auch verzweigte Alkenylgruppen enthalten. Alkenylbernsteinsäureanhydride sind beispielsweise aus α-Olefinen zugänglich, die zunächst isomerisiert werden. Dabei wird ein Gemisch aus verschiedenen Isomeren erhalten, das dann mit Maleinsäureanhydrid nach Art einer En-Reaktion zu Bernsteinsäureanhydriden umgesetzt wird. Alkenylbernsteinsäureanhydride werden gemäß der EP-A 0 593 075 durch Reaktion von Propylen- oder n-Butylenoligomeren mit Maleinsäureanhydrid hergestellt. Beispiele für diese Gruppe von Reaktivleimungs- mitteln sind Decenylbernsteinsäureanhydrid, Dodecenylbernsteinsäureanhydrid, Octe-
nylbernsteinsäureanhydrid und n-Hexadecenylbernsteinsäureanhydrid. Die einzelnen isomeren Bernsteinsäureanhydride können unterschiedliche Leimungswirkung aufweisen. So sind beispielsweise 2- und 3-Hexadecenylbernsteinsäureanhydride als Masse- leimungsmittel nicht so wirksam wie die isomeren 4-, 5-, 6-, 7- und 8- Hexadecenylbernsteinsäureanhydride.Alkenylsuccinic anhydrides are described in detail in, for example, US Pat. No. 3,102,064, EP-A 0 609 879 and EP-A 0 593 075. All alkenylsuccinic anhydrides which have hitherto been described in the literature as engine size agents for paper are also suitable according to the invention as active ingredient, either alone or in combination with alkyldiketenes. Suitable alkenylsuccinic anhydrides in the alkenyl group contain an alkyl radical having at least 6 C atoms, preferably a C 4 - to C 24 -olefin radical. Particularly preferred alkenyl succinic anhydrides contain 16 to 22, usually 16 to 18 C atoms in the alkenyl group. They may contain linear, additionally unsaturated or branched alkenyl groups. Alkenylsuccinic anhydrides are accessible for example from α-olefins, which are first isomerized. In this case, a mixture of different isomers is obtained, which is then reacted with maleic anhydride in the manner of an ene reaction to succinic anhydrides. Alkenylsuccinic anhydrides are prepared according to EP-A 0 593 075 by reaction of propylene or n-butylene oligomers with maleic anhydride. Examples of this group of reactive sizing agents are decenylsuccinic anhydride, dodecenylsuccinic anhydride, octene nylbernsteinsäureanhydrid and n-Hexadecenylbernsteinsäureanhydrid. The individual isomeric succinic anhydrides can have different sizing effect. Thus, for example, 2- and 3-hexadecenyl succinic anhydrides are not as effective as mass sizing agents as the isomeric 4-, 5-, 6-, 7- and 8-hexadecenyl succinic anhydrides.
Die in Betracht kommenden Reaktivleimungsmittel werden für die Herstellung der Komponente (a) der erfindungsgemäßen Mischungen in Wasser dispergiert. Sie werden vorzugsweise zunächst geschmolzen und danach als Schmelze in Wasser in Ge- genwart eines Tensids emulgiert, das als Dispersionsstabilisator wirkt. Das Emulgieren der Reaktivleimungsmittel kann beispielsweise durch Hochdruck-Emulgierung in den dafür bekannten Vorrichtungen, mit Hilfe der Einwirkung von Ultraschall oder durch Einwirkung starker Scherkräfte beispielsweise mit Hilfe eines Ultra-Turrax® Gerätes erfolgen.The eligible reactive sizes are dispersed in water for the preparation of component (a) of the mixtures according to the invention. They are preferably first melted and then emulsified as a melt in water in the presence of a surfactant which acts as a dispersion stabilizer. The emulsifying of the reactive sizing agent can be carried out, for example, by high-pressure emulsification in the devices known for this purpose, with the aid of the action of ultrasound or by the action of strong shearing forces, for example with the aid of an Ultra-Turrax® device.
Während des Emulgiervorgangs kann die Temperatur des Systems von 0 bis zu 130 0C, vorzugsweise bis zu 100 0C betragen. Meistens werden die Reaktivleimungsmittel in dem Temperaturbereich von 5 bis 95 0C in Wasser emulgiert, das mindestens ein Tensid enthält. Sofern man Temperaturen oberhalb von 100 0C anwendet, erfolgt der Emulgierschritt unter erhöhtem Druck in druckdichten Apparaturen. Beim Emulgieren sollte die Temperatur mindestens 5 0C, vorzugsweise mindestens 10 0C oberhalb des Schmelzpunkts bzw. oberhalb des beginnenden Erweichungsbereichs des jeweiligen Reaktivleimungsmittels liegen. Nach dem Emulgieren wird die erhaltene Öl-inWasser-Emulsion des Reaktivleimungsmittels abgekühlt, und zwar meistens auf die jeweilige Umgebungstemperatur beispielsweise 10 bis 30 0C. Man erhält entweder eine Emulsion, sofern der Schmelzpunkt des Reaktivleimungsmittels oberhalb der Temperatur des Systems liegt oder eine wässrige Dispersion, wenn die emulgierten Teilchen des Reaktivleimugnsmittels im festen Aggregatzustand vorliegen. Als Reaktivleimungsmittel werden vorzugsweise Alkylketendimere eingesetzt.During the emulsification process, the temperature of the system may be from 0 to 130 ° C., preferably up to 100 ° C. Most of the reactive size agents are emulsified in the temperature range of 5 to 95 0 C in water containing at least one surfactant. If temperatures above 100 ° C. are used, the emulsification step is carried out under elevated pressure in pressure-tight apparatus. When emulsifying the temperature should be at least 5 0 C, preferably at least 10 0 C above the melting point or above the incipient softening range of the respective reactive sizing agent. After emulsification, the resultant oil-in-water emulsion of the reactive mixture is cooled, and it was mostly to the respective ambient temperature, for example 10 to 30 0 C. This gives either an emulsion, provided that the melting point of the reactive size is above the temperature of the system or an aqueous dispersion when the emulsified particles of the reactive size are in the solid state. The reactive size agents used are preferably alkylketene dimers.
Der mittlere Durchmesser der emulgierten Teilchen des Reaktivleimungsmittels beträgt weniger als 500 nm, vorzugsweise höchstens 300 nm und liegt meistens in dem Bereich von 30 bis 300 nm, insbesondere bei 40 bis 200 nm. Die hier angegebenen Teilchengrößen der emulgierten Reaktivleimungsmittel sind gewichtsmittlere Teilchengrö- ßen, wie sie durch dynamische Lichtstreuung ermittelt werden können. Verfahren hierzu sind dem Fachmann geläufig, beispielsweise aus H. Wiese in D. Distler, Wässrige Polymerdispersionen, Wiley-VCH 1999, Kapitel 4.2.1 , S. 40ff und dort zitierte Literatur sowie H. Auweter, D. Hörn, J. Colloid Interf. Sei. 105 (1985) 399, D. Lüge, D. Hörn, Colloid Polym. Sei. 269 (1991) 704 oder H. Wiese, D. Hörn, J. Chem. Phys. 94 (1991 ) 6429.
Um eine möglichst stabile Dispersion bzw. Emulsion des Reaktivleimungsmittels zu erhalten, emulgiert man es vorzugsweise in Gegenwart mindestens eines Tensids als Dispersionsstabilisator. Meistens löst man zunächst mindestens ein Tensid in Wasser und fügt dann erst das geschmolzene Reaktivleimungsmittel zu. Man kann das Tensid jedoch auch erst während des Emulgierens oder danach zufügen. Die Zugabe des Tensids kann dabei kontinuierlich, stufenweise oder auf einmal vorgenommen werden. Man erhält eine Dispersion, die z. B. 0,01 bis 20 Gew.-%, vorzugsweise 0,1 bis 10 Gew.-% und meistens 0,2 bis 5 Gew.-% mindestens eines Tensids enthält.The mean diameter of the emulsified particles of the reactive sizing agent is less than 500 nm, preferably at most 300 nm, and is usually in the range from 30 to 300 nm, in particular from 40 to 200 nm. The particle sizes of the emulsified reactive sizing agents indicated here are weight-average particle sizes. as they can be determined by dynamic light scattering. Methods for this purpose are familiar to the person skilled in the art, for example from H. Wiese in D. Distler, Aqueous Polymer Dispersions, Wiley-VCH 1999, Chapter 4.2.1, p 40ff and literature cited therein and H. Auweter, D. Horn, J. Colloid Interf , Be. 105 (1985) 399, D. Lie, D. Horn, Colloid Polym. Be. 269 (1991) 704 or H. Wiese, D. Horn, J. Chem. Phys. 94 (1991) 6429. In order to obtain the most stable dispersion or emulsion of the reactive sizing agent, it is preferably emulsified in the presence of at least one surfactant as a dispersion stabilizer. In most cases, at least one surfactant is first dissolved in water and then the molten reactive sizing agent is first added. However, it is also possible to add the surfactant only during emulsification or afterwards. The addition of the surfactant can be carried out continuously, in stages or at once. This gives a dispersion which z. B. 0.01 to 20 wt .-%, preferably 0.1 to 10 wt .-% and usually 0.2 to 5 wt .-% of at least one surfactant.
Der Gehalt an Reaktivleimungsmittel in der wässrigen Dispersion kann beispielsweise 1 bis 60 Gew.-%, vorzugsweise 10 bis 50 Gew.-% betragen. Meistens liegt er in dem Bereich von 15 bis 30 Gew.-%.The content of reactive sizing agent in the aqueous dispersion may be, for example, 1 to 60% by weight, preferably 10 to 50% by weight. It is usually in the range of 15 to 30% by weight.
Die als Dispersionsstabilisator in Betracht kommenden Tenside können beispielsweise kationisch, anionisch, amphoter oder nichtionisch sein. Man kann ein Tensid aus einer einzigen Gruppe der genannten Tenside einsetzen oder Mischungen von Tensiden, die miteinander verträglich sind, d.h. die in wässrigem Medium nebeneinander stabil sind und keine Niederschläge bilden, beispielsweise Mischungen aus mindestens einem nichtionischen und mindestens einem anionischen Tensid, Mischungen aus mindes- tens einem nichtionischen und mindestens einem kationischen Tensid, Mischungen aus mindestens zwei kationischen Tensiden, Mischungen aus mindestens zwei anionischen Tensiden oder auch Mischungen aus mindestens zwei nichtionischen Tensiden. Als Dispersionsstabilisator kann außer einem Tensid noch zusätzlich ein Schutzkolloid und/oder ein Dispergiermittel eingesetzt werden. Geeignet sind beispielsweise Mi- schungen aus mindestens einem Tensid und mindestens einem Dispergiermittel oder Mischungen aus mindestens einem Tensid, mindestens einem Dispergiermittel und mindestens einem Schutzkolloid. Bevorzugt sind Mischungen, die zwei oder mehr Dispersionsstabilisatoren enthalten.The surfactants which are suitable as dispersion stabilizers may be, for example, cationic, anionic, amphoteric or nonionic. It is possible to use a surfactant from a single group of said surfactants or mixtures of surfactants which are compatible with each other, i. which are stable next to each other in an aqueous medium and do not form precipitates, for example mixtures of at least one nonionic and at least one anionic surfactant, mixtures of at least one nonionic and at least one cationic surfactant, mixtures of at least two cationic surfactants, mixtures of at least two anionic surfactants or mixtures of at least two nonionic surfactants. As a dispersion stabilizer, in addition to a surfactant, a protective colloid and / or a dispersant can additionally be used. For example, mixtures of at least one surfactant and at least one dispersant or mixtures of at least one surfactant, at least one dispersant and at least one protective colloid are suitable. Preferred are mixtures containing two or more dispersion stabilizers.
Als Tenside kommen beispielsweise alle oberflächenaktiven Mittel in Betracht.Suitable surfactants are, for example, all surfactants.
Beispiele für geeignete nichtionische oberflächenaktive Stoffe sind ethoxylierte Mono-, Di- und Tri-Alkylphenole (Ethoxylierungsgrad: 3 bis 50, Alkylrest: C3-C12) sowie ethoxylierte Fettalkohole (Ethoxylierungsgrad: 3 bis 80; Alkylrest: C8-C36). Beispiele hierfür sind die Marken Lutensol®der BASF AG oder die Marken Triton® der Union Carbide. Besonders bevorzugt sind ethoxylierte lineare Fettalkohole der allgemeinen FormelExamples of suitable nonionic surfactants are ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C3-C12) and also ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80, alkyl radical: C8-C36). Examples include the brands Lutensol ® from BASF AG or the Triton ® brands from Union Carbide. Particularly preferred are ethoxylated linear fatty alcohols of the general formula
n-CχH2x+i-O(CH2CH2O)y-H,n-CχH 2 x + iO (CH 2 CH 2 O) y H,
wobei x ganze Zahlen im Bereich von 10 bis 24, bevorzugt im Bereich von 12 bis 20 sind. Die Variable y steht vorzugsweise für ganze Zahlen im Bereich von 5 bis 50, besonders bevorzugt 8 bis 40. Ethoxylierte lineare Fettalkohole liegen üblicherweise als
Gemisch verschiedener ethoxylierter Fettalkohole mit unterschiedlichem Ethoxylie- rungsgrad vor. Die Variable y steht im Rahmen der vorliegenden Erfindung für den Mittelwert (Zahlenmittel). Geeignete nichtionische oberflächenaktive Substanzen sind weiterhin Copolymere, insbesondere Blockcopolymere von Ethylenoxid und wenigs- tens einem C3-Cio-Alkylenoxid, z.B. Triblockcopolymere der Formelwhere x are integers in the range of 10 to 24, preferably in the range of 12 to 20. The variable y preferably stands for integers in the range of 5 to 50, more preferably 8 to 40. Ethoxylated linear fatty alcohols are usually as Mixture of different ethoxylated fatty alcohols with different degree of ethoxylation ago. The variable y in the context of the present invention stands for the mean value (number average). Suitable nonionic surface-active substances are also copolymers, in particular block copolymers of ethylene oxide and at least one C 3 -C 10 -alkylene oxide, for example triblock copolymers of the formula
RO(CH2CH2θ)yi-(BO)y2-(A-O)m-(BO)y3-(CH2CH2O)y4R'.RO (CH 2 CH 2 O) yi- (BO) y 2 - (AO) m - (BO) y 3 - (CH 2 CH 2 O) y 4 R '.
worin m für 0 oder 1 steht, A für einen von einem aliphatischen, cycloaliphatischen o- der aromatischen Diol, abgeleiteten Rest, z.B. für Ethan-1 ,2-diyl, propan-1 ,3-diyl, Bu- tan-1 ,4-diyl, Cyclohexan-1 ,4-diyl, Cyclohexan-1 ,2-diyl oder Bis(cylohexyl)methan-4,4'- diyl steht, B und B' unabhängig voneinander Propan-1 ,2-diyl, Butan-1 ,2-diyl oder Phe- nylethanyl y2 und y3 unabhängig voneinander für eine Zahl von 2 bis 100 stehen, y1 und y4 unabhängig voneinander für eine Zahl von 2 bis 100 stehen, wobei die Summe y1 + y2 + y3 + y4 vorzugsweise im Bereich von 20 bis 400 steht, was einem zahlenmittleren Molekulargewicht im Bereich von 1000 bis 20000 entspricht. Vorzugsweise steht A für Ethan-1 ,2-diyl, Propan-1 ,3-diyl oder Butan-1 ,4-diyl. B steht vorzugsweise für Propan-1 ,2-diyl.wherein m is 0 or 1, A is a radical derived from an aliphatic, cycloaliphatic or aromatic diol, e.g. for ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, cyclohexane-1, 4-diyl, cyclohexane-1, 2-diyl or bis (cylohexyl) methane-4 , 4'-diyl, B and B 'independently of one another propan-1, 2-diyl, butane-1, 2-diyl or Phe- nylethanyl y2 and y3 independently represent a number from 2 to 100, y1 and y4 independently from each other represent a number from 2 to 100, wherein the sum y1 + y2 + y3 + y4 is preferably in the range of 20 to 400, which corresponds to a number average molecular weight in the range of 1000 to 20,000. Preferably A is ethane-1, 2-diyl, propane-1, 3-diyl or butane-1, 4-diyl. B is preferably propane-1,2-diyl.
Als oberflächenaktive Substanzen kommen außer den nichtionischen Tensiden auch anionische und kationische Tenside in Betracht. Sie können allein oder als Mischung eingesetzt werden. Voraussetzung dafür ist allerdings, dass sie miteinander verträglich sind. Diese Voraussetzung trifft beispielsweise für Mischungen aus jeweils einer Verbindungsklasse sowie für Mischungen aus nichtionischen und anionischen Tensiden und Mischungen aus nichtionischen und kationischen Tensiden zu. Beispiele für geeignete anionische oberflächenaktive Mittel sind Natriumlaurylsulfat, Natriumdodecyl- sulfat, Natriumhexadecylsulfat und Natriumdioctylsulfosuccinat.Suitable surface-active substances besides the nonionic surfactants are anionic and cationic surfactants. They can be used alone or as a mixture. The prerequisite for this, however, is that they are compatible with each other. This requirement applies, for example, to mixtures of one compound class in each case and to mixtures of nonionic and anionic surfactants and mixtures of nonionic and cationic surfactants. Examples of suitable anionic surfactants are sodium lauryl sulfate, sodium dodecyl sulfate, sodium hexadecyl sulfate and sodium dioctyl sulfosuccinate.
Beispiele für kationische Tenside sind quartäre Alkylammoniumsalze, Alkylbenzylam- moniumsalze, wie Dimethyl-Ci2- bis Cis-alkylbenzylammoniumchloride, primäre, sekundäre und tertiäre Fettaminsalze, quartäre Amidoaminverbindungen, Alkylpyridini- umsalze, Alkylimidazoliniumsalze und Alkyloxazoliniumsalze.Examples of cationic surfactants are quaternary alkylammonium salts, alkylbenzylammonium salts, such as dimethyl-C 2 - to cis-alkylbenzylammonium chlorides, primary, secondary and tertiary fatty amine salts, quaternary amidoamine compounds, alkylpyridinium salts, alkylimidazolinium salts and alkyloxazolinium salts.
Besonders bevorzugt sind anionische Tenside, wie z. B. mit Schwefelsäure veresterte (gegebenenfalls alkoxylierte) Alkohole, die meistens in mit Alkalilauge neutralisierter Form verwendet werden. Weitere übliche Emulgatoren sind beispielsweise Natriumal- kylsulfonate, Natriumalkylsulfate wie z. B. Natriumlaurylsulfat, Natriumdodecylbenzol- sulfonat, Sulfobernsteinsäureester. Weiterhin können als anionische Emulgatoren auch Ester der Phoshorsäure oder der phosphorigen Säure sowie aliphatische oder aromati- sehe Carbonsäuren verwendet werden. Übliche Emulgatoren sind in der Literatur eingehend beschrieben, siehe beispielsweise M. Ash, I. Ash, Handbook of Industrial Surfactants, Third Edition, Synapse Information Resources Inc.
Die Komponente (a) der Papierleimungsmittelmischungen ist vorzugsweise erhältlich durch Emulgieren eines Reaktivleimungsmittels in Gegenwart eines Tensids und mindestens eines Dispergiermittels und/oder mindestens eines Schutzkolloids. Häufig verwendete Dispergiermittel sind beispielsweise Kondensate aus Naphthalinsulfonsäu- re und Formaldehyd, Kondensate aus einem Salz der Naphthalinsulfonsäure oder Ligninsulfonsäure bzw. deren Salze. Als Salze von Naphthalinsulfonsäure und von Ligninsulfonsäure kommen vorzugsweise die vollständig oder partiell mit Natronlauge, Kalilauge, Ammoniak oder Calciumhydroxid neutralisierten Produkte in Betracht. Als Dispergiermittel können jedoch auch amphiphile Polymere oder Nanopartikeln aus wasserunlöslichen organischen Polymeren oder aus wasserunlöslichen anorganischen Verbindungen (Pickering-Effekt) eingesetzt werden. Stabilisatoren dieser Art sind z.B. nanoscaliges Siliciumdioxid und nanoscaliges Aluminiumoxid.Particularly preferred are anionic surfactants, such as. B. with sulfuric acid esterified (optionally alkoxylated) alcohols, which are usually used in neutralized with alkali lye form. Further customary emulsifiers are, for example, sodium alkyl sulfonates, sodium alkyl sulfates, such as, for example, sodium. For example, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sulfosuccinic. Furthermore, as anionic emulsifiers and esters of phosphoric acid or phosphorous acid and aliphatic or aromatic see carboxylic acids can be used. Common emulsifiers are well described in the literature, see, for example, M. Ash, I. Ash, Handbook of Industrial Surfactants, Third Edition, Synapse Information Resources Inc. The component (a) of the paper size mixtures is preferably obtainable by emulsifying a reactive sizing agent in the presence of a surfactant and at least one dispersant and / or at least one protective colloid. Frequently used dispersants are, for example, condensates of naphthalenesulfonic acid and formaldehyde, condensates of a salt of naphthalenesulfonic acid or ligninsulfonic acid or salts thereof. Suitable salts of naphthalenesulfonic acid and lignosulfonic acid are preferably the products completely or partially neutralized with sodium hydroxide solution, potassium hydroxide solution, ammonia or calcium hydroxide. However, amphiphilic polymers or nanoparticles of water-insoluble organic polymers or of water-insoluble inorganic compounds (Pickering effect) can also be used as dispersants. Stabilizers of this type are, for example, nanoscale silica and nanoscale alumina.
Die Komponente (a) der erfindungsgemäßen Mischungen ist daher erhältlich durch Emulgieren eines Reaktivleimungsmittels in Gegenwart eines Tensids und mindestens eines Dispergiermittels aus der Gruppe der Kondensate aus Naphthalinsulfonsäure und/oder deren Salzen und Formaldehyd, Ligninsulfonsäure oder deren Salzen, amphiphilen Polymere und/oder Nanopartikeln aus organischen Polymeren oder aus anorganischen Verbindungen.The component (a) of the mixtures according to the invention is therefore obtainable by emulsifying a reactive sizing agent in the presence of a surfactant and at least one dispersant selected from the group consisting of condensates of naphthalenesulfonic acid and / or salts and formaldehyde, lignosulfonic acid or its salts, amphiphilic polymers and / or nanoparticles organic polymers or inorganic compounds.
Die als Dispergiermittel eingesetzten amphiphilen Polymere können eine mittlere Molmasse Mw von beispielsweise 1000 bis 100 000 haben. Sie werden in Kombination mit einem Tensid als Dispersionsstabilisator verwendet. Beispiele für amphiphile Polymere sind Copolymerisate, die Einheiten vonThe amphiphilic polymers used as dispersants may have an average molecular weight Mw of, for example, 1000 to 100,000. They are used in combination with a surfactant as a dispersion stabilizer. Examples of amphiphilic polymers are copolymers comprising units of
(i) hydrophoben monoethylenisch ungesättigten Monomeren und (ii) monoethylenisch ungesättigten Carbonsäuren, monoethylenisch ungesättigten Sulfonsäuren, monoethylenisch ungesättigten Phosphonsäuren oder deren Mi- schungen und/oder basischen Monomeren(i) hydrophobic monoethylenically unsaturated monomers and (ii) monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated sulfonic acids, monoethylenically unsaturated phosphonic acids or mixtures thereof and / or basic monomers
enthalten.contain.
Geeignete hydrophobe monoethylenisch ungesättigte Monomere zur Herstellung der amphiphilen Polymerisate sind beispielsweiseSuitable hydrophobic monoethylenically unsaturated monomers for preparing the amphiphilic polymers are, for example
(i) Styrol, Methylstyrol, Ethylstyrol, Acrylnitril, Methacrylnitril, C2- bis Cis-Olefine, Ester aus monoethylenisch ungesättigten C3- bis Cs-Carbonsäuren und einwertigen Alkoholen, Vinylalkylether, Vinylester oder deren Mischungen. Aus dieser Gruppe von Monomeren verwendet man vorzugsweise Isobuten, Diisobuten,(i) styrene, methylstyrene, ethylstyrene, acrylonitrile, methacrylonitrile, C 2 to C 6 olefins, esters of monoethylenically unsaturated C 3 to C 8 carboxylic acids and monohydric alcohols, vinyl alkyl ethers, vinyl esters or mixtures thereof. Isobutene, diisobutene, is preferably used from this group of monomers.
Styrol und Acrylsäureester wie Ethylacrylat, Isopropylacrylat, n-Butylacrylat und sec.-Butylacrylat.
Die amphiphilen Copolymerisate enthalten als hydrophile Monomere vorzugsweiseStyrene and acrylic acid esters such as ethyl acrylate, isopropyl acrylate, n-butyl acrylate and sec-butyl acrylate. The amphiphilic copolymers are preferably contained as hydrophilic monomers
(ii) Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid, Itaconsäure, Vinylsulfonsäure, 2-Acrylamidomethylpropansulfonsäure, Acrylamido-propan-3- sulfonsäure, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat, Styrolsulfonsäure, Vinylphosphonsäure oder deren Mischungen in einpolymerisierter Form. Die sauren Monomeren können in Form der freien Säuren oder in partiell oder vollständig neutralisierter Form vorliegen.(ii) acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, vinylsulfonic acid, 2-acrylamidomethylpropanesulfonic acid, acrylamido-propane-3-sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, styrenesulfonic acid, vinylphosphonic acid or mixtures thereof in copolymerized form. The acidic monomers may be in the form of the free acids or in partially or completely neutralized form.
Weitere geeignete hydrophile Monomere sind basische Monomere. Sie können mit den hydrophoben Monomeren (i) allein oder auch in Mischung mit vorstehend genannten den sauren Monomeren polymerisiert werden. Wenn man Mischungen aus basischen und sauren Monomeren einsetzt, entstehen amphotere Copolymerisate, die je nach Molverhältnis der jeweils einpolymerisierten sauren zu basischen Monomeren anionisch oder kationisch geladen sind.Other suitable hydrophilic monomers are basic monomers. They may be polymerized with the hydrophobic monomers (i) alone or in admixture with the above acidic monomers. When mixtures of basic and acidic monomers are used, amphoteric copolymers are formed, which are anionically or cationically charged, depending on the molar ratio of the copolymerized acidic to basic monomers.
Basische Monomere sind beispielsweise Di-d-bis C2-alkylamino-C2-bis C4- alkyl(meth)acrylate oder Diallyldimethylammoniumchlorid. Die basischen Monomeren können in Form der freien Basen, der Salze mit organischen oder anorganischen Säuren oder in der mit Alkylhalogeniden quaternierten Form vorliegen. Die Salzbildung bzw. die Quaternierung, bei der die basischen Monomeren kationisch werden, kann teilweise oder vollständig erfolgt sein. Beispiele für solche Verbindungen sind Dimethy- laminoethylmethacrylat, Diethylaminoethylmethacrylat, Dimethylaminoethylacrylat, Diethylaminoethylacrylyat, Dimethylaminopropylmethacrylat, Dimethylaminopropylacry- lat, Diethylaminopropylmethacrylat, Diethylaminopropylacrylat und/oder Dimethylami- noethylacrylamid, Dimethylaminoethylmethacrylamid, Dimethylaminopropylacrylamid, Dimethylaminopropylmethacrylamid und/oder Diallyldimethylammoniumchlorid.Basic monomers are, for example, di-C 1 to C 2 -alkylamino-C 2 to C 4 -alkyl (meth) acrylates or diallyldimethylammonium chloride. The basic monomers may be in the form of the free bases, the salts with organic or inorganic acids or in the form quaternized with alkyl halides. The salt formation or the quaternization, at which the basic monomers become cationic, can be partial or complete. Examples of such compounds are dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, diethylaminopropyl methacrylate, diethylaminopropyl acrylate and / or dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and / or diallyldimethylammonium chloride.
Sofern die amphiphilen Copolymerisate in Form der freien Säure nicht ausreichend wasserlöslich sind, werden sie in Form von wasserlöslichen Salzen eingesetzt, z. B. verwendet man die entsprechenden Alkalimetall-, Erdalkalimetall- und Ammoniumsalze. Diese Salze werden beispielsweise durch partielle oder vollständige Neutralisation der freien Säuregruppen der amphiphilen Copolymerisate mit Basen hergestellt, z. B. verwendet man zur Neutralisation Natronlauge, Kalilauge, Magnesiumoxid, Ammoniak oder Amine wie Triethanolamin, Ethanolamin, Morpholin, Triethylamin oder Butylamin. Vorzugsweise werden die Säuregruppen der amphiphilen Copolymerisate mit Ammoniak oder Natronlauge neutralisiert. Die Wasserlöslichkeit von basischen Monomeren bzw. von Copolymerisaten, die solche Monomere einpolymerisiert enthalten, kann da- gegen durch partielle oder vollständige Neutralisation mit einer Mineralsäure wie Salzsäure oder Schwefelsäure oder durch Zusatz einer organischen Säure wie Essigsäure oder p-Toluolsulfonsäure, erhöht werden. Die Molmasse der amphiphilen Copolymeri-
säte beträgt beispielsweise 1000 bis 100 000 und liegt vorzugsweise in dem Bereich von 1500 bis 10 000. Die Säurezahlen der amphiphilen Copolymerisate betragen beispielsweise 50 bis 500, vorzugsweise 150 bis 350 mg KOH/g Polymer.If the amphiphilic copolymers in the form of the free acid are not sufficiently soluble in water, they are used in the form of water-soluble salts, for. B. using the corresponding alkali metal, alkaline earth metal and ammonium salts. These salts are prepared, for example, by partial or complete neutralization of the free acid groups of the amphiphilic copolymers with bases, e.g. For example, sodium hydroxide solution, potassium hydroxide solution, magnesium oxide, ammonia or amines such as triethanolamine, ethanolamine, morpholine, triethylamine or butylamine are used for neutralization. Preferably, the acid groups of the amphiphilic copolymers are neutralized with ammonia or sodium hydroxide solution. The water solubility of basic monomers or of copolymers which contain such monomers in copolymerized form can be increased by partial or complete neutralization with a mineral acid such as hydrochloric acid or sulfuric acid or by addition of an organic acid such as acetic acid or p-toluenesulfonic acid. The molecular weight of the amphiphilic copolymer The acid numbers of the amphiphilic copolymers are, for example, 50 to 500, preferably 150 to 350 mg KOH / g of polymer.
Bevorzugt sind solche amphiphilen Copolymerisate, diePreference is given to those amphiphilic copolymers which
(i) 95 bis 45 Gew.-% Isobuten, Diisobuten, Styrol oder deren Mischungen und (ii) 5 bis 55 Gew.-% Acrylsäure, Methacrylsäure, Maleinsäure, Halbester von Maleinsäure oder deren Mischungen(I) 95 to 45 wt .-% of isobutene, diisobutene, styrene or mixtures thereof and (ii) 5 to 55 wt .-% acrylic acid, methacrylic acid, maleic acid, half esters of maleic acid or mixtures thereof
einpolymerisiert enthalten, wobei meistens solche Copolymerisate als Dispergiermittel eingesetzt werden, diecontain copolymerized, with most such copolymers are used as dispersants, the
(i) 45 bis 80 Gew.-% Styrol, (ii) 55 bis 20 Gew.-% Acrylsäure und gegebenenfalls (iii) zusätzlich weitere Monomere(i) 45 to 80% by weight of styrene, (ii) 55 to 20% by weight of acrylic acid and, if appropriate, (iii) additionally further monomers
einpolymerisiert enthalten. Die Copolymerisate können gegebenenfalls als weitere Monomere (iii) Einheiten von Maleinsäurehalbestern einpolymerisiert enthalten. Solche Copolymerisate sind beispielsweise dadurch erhältlich, daß man Copolymerisate aus Styrol, Diisobuten oder Isobuten oder deren Mischungen mit Maleinsäureanhydrid in Abwesenheit von Wasser copolymerisiert und die Copolymerisate im Anschluß an die Polymerisation mit Alkoholen umsetzt, wobei man pro Mol Anhydridgruppen im Copo- lymerisat 5 bis 50 Mol-% eines einwertigen Alkohols einsetzt. Geeignete Alkohole sind beispielsweise Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol und tert.-Butanol. Man kann jedoch auch die Anhydridgruppen der Copolymerisate mit mehrwertigen Alkoholen wie Glykol oder Glycerin umsetzen. Hierbei wird die Reaktion jedoch nur soweit geführt, daß nur eine OH-Gruppe des mehrwertigen Alkohols mit der Anhydridgruppe reagiert. Sofern die Anhydridgruppen der Copolymerisate nicht voll- ständig mit Alkoholen umgesetzt werden, erfolgt die Ringöffnung der nicht mit Alkoholen umgesetzten Anhydridgruppen durch Zugabe von Wasser.incorporated in copolymerized form. The copolymers may optionally contain, as further monomers (iii), units of maleic monoesters in copolymerized form. Such copolymers are obtainable, for example, by copolymerizing copolymers of styrene, diisobutene or isobutene or mixtures thereof with maleic anhydride in the absence of water and reacting the copolymers with alcohols after the polymerization, with from 5 to 50 per mole of anhydride groups in the copolymer Mol% of a monohydric alcohol. Suitable alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol. However, it is also possible to react the anhydride groups of the copolymers with polyhydric alcohols, such as glycol or glycerol. However, the reaction is carried out only to the extent that only one OH group of the polyhydric alcohol reacts with the anhydride group. If the anhydride groups of the copolymers are not completely reacted with alcohols, the ring opening of the anhydride groups not reacted with alcohols is effected by addition of water.
Andere geeignete Dispersionsstabilisatoren sind Mischungen aus mindestens einem Tensid und beispielsweise handelsüblichen Polymerisaten von monoethylenisch unge- sättigten Säuren sowie Pfropfpolymerisate von N-Vinylformamid auf Polyalkylenglyko- len, die beispielsweise in der WO 96/34903 beschrieben werden. Die aufgepfropften Vinylformamideinheiten können gegebenenfalls unter Bildung von Vinylamineinheiten hydrolysiert sein. Der Anteil an aufgepfropften Vinylformamideinheiten beträgt vorzugsweise 20 bis 40 Gew.-%, bezogen auf Polyalkylenglykol. Vorzugsweise verwendet man Polyethylenglykole mit Molmassen von 2000 bis 10 000.
Außerdem kommen als Dispersionsstabilisator Mischungen aus mindestens einem Tensid und zwitterionischen Polyalkylenpolyaminen und/oder zwitterionischen Polye- thyleniminen in Betracht. Solche Verbindungen sind beispielsweise aus der EP-B 0 1 12 592 bekannt. Sie sind beispielsweise dadurch erhältlich, daß man ein Po- lyalkylenpolyamin oder Polyethylenimin zunächst alkoxyliert, z. B. mit Ethylenoxid, Propylenoxid und/oder Butylenoxid und die Alkoxylierungsprodukte anschließend qua- ternisiert, z.B. mit Methylbromid oder Dimethylsulfat und die quaternierten, alkoxylier- ten Produkte dann mit Chlorsulfonsäure oder Schwefeltrioxid sulfatiert. Die Molmasse der zwitterionischen Polyalkylenpolyamine beträgt beispielsweise 1000 bis 9000 vor- zugsweise 1500 bis 7500. Die zwitterionischen Polyethylenimine haben vorzugsweise Molmassen in dem Bereich von 1500 bis 7500 Dalton.Other suitable dispersion stabilizers are mixtures of at least one surfactant and, for example, commercially available polymers of monoethylenically unsaturated acids and also graft polymers of N-vinylformamide on polyalkylene glycols, which are described, for example, in WO 96/34903. The grafted vinylformamide units may optionally be hydrolyzed to form vinylamine units. The proportion of grafted vinylformamide units is preferably 20 to 40 wt .-%, based on polyalkylene glycol. Polyethylene glycols having molecular weights of 2,000 to 10,000 are preferably used. Other suitable dispersion stabilizers are mixtures of at least one surfactant and zwitterionic polyalkylenepolyamines and / or zwitterionic polyethyleneimines. Such compounds are known for example from EP-B 0 1 12 592. They are obtainable, for example, by first alkoxylating a polyalkylene polyamine or polyethyleneimine, eg. For example, with ethylene oxide, propylene oxide and / or butylene oxide and the alkoxylation subsequently quaternized, eg with methyl bromide or dimethyl sulfate and the quaternized, alkoxylated products then sulfated with chlorosulfonic acid or sulfur trioxide. The molar mass of the zwitterionic polyalkylenepolyamines is, for example, 1000 to 9000, preferably 1500 to 7500. The zwitterionic polyethyleneimines preferably have molecular weights in the range from 1500 to 7500 daltons.
Die Komponente (a) der Papierleimungsmittelmischungen ist auch mit Vorteil dadurch erhältlich, dass man ein Reaktivleimungsmittel in Gegenwart eines Tensids und min- destens eines Schutzkolloids emulgiert, das beispielsweise ausgewählt ist aus derComponent (a) of the paper size mixtures is also advantageously obtainable by emulsifying a reactive sizing agent in the presence of a surfactant and at least one protective colloid, which is for example selected from
Gruppe der Polyvinylalkohole, Polyvinylpyrrolidone, Polyacrylsäuren, Polyalkylenglyko- Ie, ein- oder beidseitig mit Alkyl-, Carboxyl- oder Aminogruppen endgruppenverschlos- senen Polyalkylenglykole, Polydiallyldimethylammoniumchloride, wasserlöslichen Stärken, wasserlöslichen Stärkederivate und/oder wasserlöslichen Proteine. Die Schutzkol- loide haben in der Regel mittlere Molmassen Mw von oberhalb 500, vorzugsweise von mehr als 1000 bis höchstens 100 000, meistens bis 60 000. Außer den genannten Schutzkolloiden kommen beispielsweise wasserlösliche Cellulosederivate wie Carbo- xymethylcellulose und Pfropfpolymerisate von Vinylacetat und/oder Vinylpropionat auf Polyethylenglykolen und/oder Polysacchariden in Betracht. Wasserlösliche Stärken, Stärkederivate und Proteine werden beispielsweise beschrieben in Römpp, Chemie Lexikon 9. Auflage, Band 5, Seite 3569 oder in Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band 14/2 Kapitel IV Umwandlung von Cellulose und Stärke von E. Husemann und R. Werner, Seiten 862 - 915 und in Ullmanns Encyclopedia for Industrial Chemistry, 6. Auflage, Band 28, Seiten 533 ff unter Polysaccharides.Group of polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acids, polyalkylene glycols, polyalkylene glycols terminated on one or both sides with alkyl, carboxyl or amino groups, polydiallyldimethylammonium chlorides, water-soluble starches, water-soluble starch derivatives and / or water-soluble proteins. The protective colloids generally have average molecular weights M w of above 500, preferably of more than 1000 to at most 100 000, usually up to 60 000. In addition to the protective colloids mentioned, for example, water-soluble cellulose derivatives such as carboxymethylcellulose and graft polymers of vinyl acetate and / or Vinyl propionate on polyethylene glycols and / or polysaccharides into consideration. Water-soluble starches, starch derivatives and proteins are described, for example, in Römpp, Chemie Lexikon 9th Edition, Volume 5, page 3569 or in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/2, Chapter IV Conversion of Cellulose and Starch of E. Husemann and R. Werner, pages 862-915 and in Ullmann's Encyclopedia for Industrial Chemistry, 6th edition, volume 28, pages 533 ff under polysaccharides.
Geeignete Schutzkolloide sind insbesondere alle Arten von wasserlöslicher Stärke, z. B. sowohl Amylose als auch Amylopektin, native Stärken, hydrophob oder hydrophil modifizierte Stärken, anionische Stärken, kationisch modifizierte Stärken, Maltodextri- ne, abgebaute Stärken, wobei der Stärkeabbau beispielsweise oxidativ, thermisch, hydrolytisch oder enzymatisch vorgenommen werden kann und wobei für den Stärkeabbau sowohl native als auch modifizierte Stärken eingesetzt werden können. Weitere geeignete Schutzkolloide sind Dextrine und vernetzte wasserlösliche Stärken, die was- serquellbar sind.Suitable protective colloids are in particular all types of water-soluble starch, for. For example, both amylose and amylopectin, native starches, hydrophobically or hydrophilically modified starches, anionic starches, cationically modified starches, maltodextri- ne, degraded starches, wherein the starch degradation can be carried out, for example, oxidatively, thermally, hydrolytically or enzymatically and wherein for the starch degradation both native and modified starches can be used. Other suitable protective colloids are dextrins and crosslinked water-soluble starches which are water-swellable.
Vorzugsweise setzt man als Schutzkolloid native, wasserlösliche Stärken ein, die beispielsweise mit Hilfe eines Stärkeaufschlusses in eine wasserlösliche Form überführt werden können sowie anionisch modifizierte Stärken wie oxidierte Kartoffelstärke. Be-
sonders bevorzugt werden anionisch modifizierte Stärken, die einem Molekulargewichtsabbau unterworfen wurden. Der Molekulargewichtsabbau wird vorzugsweise enzymatisch durchgeführt. Die mittlere Molmasse Mw der abgebauten Stärken beträgt beispielsweise 500 bis 100 000, vorzugsweise 1000 bis 30 000. Die abgebauten Stär- ken haben beispielsweise eine intrinsische Viskosität [η] von 0,04 bis 0,5 dl/g. Solche Stärken werden beispielsweise in der EP-B 0 257 412 und in der EP-B 0 276 770 beschrieben. Falls bei der Polymerisation Schutzkolloide eingesetzt werden, betragen die angewendeten Mengen beispielsweise 0,5 bis 50, insbesondere 5 bis 40 Gew.-%, meistens 10 bis 30 Gew.-%, bezogen auf die bei der Polymerisation eingesetzten Mo- nomeren.Native, water-soluble starches which can be converted into a water-soluble form, for example by means of starch digestion, and anionically modified starches, such as oxidized potato starch, are preferably used as the protective colloid. loading Particularly preferred are anionically modified starches which have been subjected to a reduction in molecular weight. The molecular weight degradation is preferably carried out enzymatically. The average molecular weight M w of the degraded starches is, for example, 500 to 100,000, preferably 1,000 to 30,000. The degraded starches have, for example, an intrinsic viscosity [η] of 0.04 to 0.5 dl / g. Such starches are described, for example, in EP-B 0 257 412 and in EP-B 0 276 770. If protective colloids are used in the polymerization, the amounts used are, for example, from 0.5 to 50, in particular from 5 to 40, preferably from 10 to 30,% by weight, based on the monomers used in the polymerization.
Besonders bevorzugte Dispersionsstabilisatoren sind Kombinationen aus mindestens einem Tensid und aus mindestens einer abgebauten nativen Stärke oder mindestens einer wasserlöslichen kationischen Stärke sowie Mischungen aus mindestens einem Tensid und einem Dispergiermittel aus einem Kondensat aus Naphthalinsulfonsäure und Formaldehyd. Die Kondensate aus Naphthalinsulfonsäure und Formaldehyd können gegebenenfalls noch durch Einkondensieren von Harnstoff modifiziert sein. Die Kondensate können in Form der freien Säuren sowie in partiell oder in vollständig neutralisierter Form eingesetzt werden. Als Neutralisationsmittel kommen vorzugsweise Natronlauge, Kalilauge, Ammoniak, Natriumhydrogencarbonat, Natriumcarbonat oder Kaliumcarbonat in Betracht. Auch Ligninsulfonsäure oder deren Salze sind als Dispergiermittel geeignet. Außer den genannten Neutralisationsmitteln für Naphthalinsulfonsäure kommt für die partielle oder vollständige Neutralisation von Ligninsulfonsäure noch Calciumhydroxid bzw. Calciumoxid in Betracht.Particularly preferred dispersion stabilizers are combinations of at least one surfactant and at least one degraded native starch or at least one water-soluble cationic starch and mixtures of at least one surfactant and a dispersant of a condensate of naphthalenesulfonic acid and formaldehyde. The condensates of naphthalenesulfonic acid and formaldehyde may optionally be modified by condensing urea. The condensates can be used in the form of the free acids as well as in partially or completely neutralized form. Suitable neutralizing agents are preferably sodium hydroxide solution, potassium hydroxide solution, ammonia, sodium bicarbonate, sodium carbonate or potassium carbonate. Lignosulfonic acid or its salts are also suitable as dispersants. Apart from the neutralizing agents mentioned for naphthalenesulfonic acid, calcium hydroxide or calcium oxide is also suitable for the partial or complete neutralization of lignin sulfonic acid.
Die Komponente (a) der erfindungsgemäßen Mischungen ist vorzugsweise erhältlich durch Emulgieren eines Reaktivleimungsmittels in Gegenwart eines anionischen Ten- sids und mindestens eines Dispergiermittels aus einem Kondensat aus Naphthalinsulfonsäure und Formaldehyd und gegebenenfalls mindestens eines Schutzkolloids.The component (a) of the mixtures according to the invention is preferably obtainable by emulsifying a reactive sizing agent in the presence of an anionic surfactant and at least one dispersant of a condensate of naphthalenesulfonic acid and formaldehyde and optionally at least one protective colloid.
Die oben beschriebenen wässrigen Dispersionen eines Reaktivleimungsmittels sind stabil. Sie werden zur Herstellung der erfindungsgemäßen Papierleimungsmittel- mischungen mit mindestens einer wässrigen Dispersion eines Emulsionspolymerisats aus mindestens einem ethylenisch ungesättigten Monomeren (Komponente (b) der erfindungsgemäßen Mischungen) gemischt. Das Mischen der Dispersionen kann beispielsweise in einem Behälter vorgenommen werden, in dem beispielsweise die Komponente (a) der Mischung (Dispersion eines Reaktivleimungsmittels) vorlegt und dazu unter Rühren die wässrige Dispersion eines Emulsionspolymerisates (Komponente (b)) dosiert. Man kann die Komponente (b) kontinuierlich, stufenweise oder auf einmal zu der Vorlage zugeben. Die erfindungsgemäßen Mischungen sind auch erhältlich, wenn man die Komponente (b) in einem Behälter vorlegt und die Komponente (a) kontinuierlich, stufenweise oder auf einmal in die Vorlage dosiert. Ebenso ist es möglich, beide
Komponenten kontinuierlich mit Hilfe einer Zweistoffdüse oder eines statischen Mischers zu vereinigen. Die Temperatur kann während des Mischvorgangs in einem weiten Bereich schwanken. Sie liegt beispielsweise bei 10 bis 95, meistens bei 15 bis 600C. Überlicherweise erfolgt das Mischen der beiden Komponenten (a) und (b) bei der jeweiligen Raumtemperatur. Man erhält eine wässrige Dispersion, in der die dispergier- ten Bestandteile der Komponenten (a) und (b) getrennt nebeneinander vorliegen. Das Gewichtsverhältnis der Komponenten (a) und (b) beträgt in den erfindungsgemäßen Mischungen insbesondere 5 : 1 bis 1 : 5. In Abhängigkeit von der Menge und Art der zu Stabilisierung der Dispersion der Reaktivleimungsmittel verwendeten Tenside, Disper- giermittel und/oder Schutzkolloide haben diese Dispersionen eine anionische oder kationische Ladung bzw. sind nicht geladen. Der pH-Wert der wässrigen Dispersionen der Reaktivleimungsmittel beträgt beispielsweise 2 bis 7, vorzugsweise 3 bis 5.The aqueous dispersions of a reactive sizing agent described above are stable. They are mixed with at least one aqueous dispersion of an emulsion polymer of at least one ethylenically unsaturated monomer (component (b) of the mixtures according to the invention) to prepare the paper size compositions of the invention. The mixing of the dispersions can be carried out, for example, in a container in which, for example, component (a) is introduced into the mixture (dispersion of a reactive sizing agent) and the aqueous dispersion of an emulsion polymer (component (b)) is metered in with stirring. Component (b) can be added continuously, stepwise or all at once to the original. The mixtures according to the invention are also obtainable if the component (b) is initially introduced in a container and the component (a) is metered into the original continuously, in stages or at once. Likewise it is possible both To combine components continuously with the help of a two-fluid nozzle or a static mixer. The temperature can fluctuate during the mixing process in a wide range. It is, for example, at 10 to 95, usually at 15 to 60 0 C. Usually, the mixing of the two components (a) and (b) takes place at the respective room temperature. An aqueous dispersion is obtained in which the dispersed constituents of components (a) and (b) are present separately next to one another. The weight ratio of components (a) and (b) in the mixtures according to the invention is in particular 5: 1 to 1: 5. Depending on the amount and nature of the surfactants used to stabilize the dispersion of the reactive sizes, dispersants and / or protective colloids these dispersions are an anionic or cationic charge or are not charged. The pH of the aqueous dispersions of the reactive sizes is, for example, 2 to 7, preferably 3 to 5.
Wässrige Dispersionen von Emulsionspolymerisaten aus mindestens einem ethyle- nisch ungesättigten Monomeren (Komponente (b) der erfindungsgemäßen Mischungen) sind bekannt. Sie werden durch Polymerisieren der Monomeren in wässrigem Medium in Gegenwart grenzflächenaktiven Verbindungen und von Radikale bildenden Polymerisationsinitiatoren hergestellt. Als Emulsionspolymerisate kommen beispielsweise Polymere in Betracht, die zu mindestens 40 Gew.-% aus sogenannten Haupt- monomeren, ausgewählt aus d- bis C2o-Alkyl(meth)acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden gesättigten Carbonsäuren, Vinylaromaten mit bis zu 20 C- Atomen, ethylenisch ungesättigten Nitrilen, Vinylhalogeniden, Vinylethern von 1 bis 10 C-Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoffen mit 2 bis 8 C- Atomen und ein oder zwei Doppelbindungen oder Mischungen dieser Monomeren auf- gebaut sind.Aqueous dispersions of emulsion polymers of at least one ethylenically unsaturated monomer (component (b) of the mixtures according to the invention) are known. They are prepared by polymerizing the monomers in an aqueous medium in the presence of surfactants and radical-forming polymerization initiators. Suitable emulsion polymers are, for example, polymers comprising at least 40% by weight of so-called main monomers selected from C 1 - to C 20 -alkyl (meth) acrylates, vinyl esters of saturated carboxylic acids containing up to 20 C atoms, vinylaromatics having bis to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers containing from 1 to 10 C-atoms alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers are built up.
Vorzugsweise handelt es sich bei den Emulsionspolymerisaten um ein Polymer, das zu mindestens 70 Gew.-%, besonders bevorzugt zu mindestens 95 Gew.-% aus sogenannten Hauptmonomeren besteht, die in Wasser emulgierbar sind.The emulsion polymers are preferably a polymer which consists of at least 70% by weight, particularly preferably at least 95% by weight, of so-called main monomers which are emulsifiable in water.
Beispiele für Hauptmonomere sind neutrale, monoethylenisch ungesättigte Monomere aus der Gruppe der vinylaromatischen Monomere wie Styrol, α-Methylstyrol, tert- Butylstyrol und Vinyltoluol, Ester α,ß-monoethylenisch ungesättigter Mono- und Dicar- bonsäuren mit 3 bis 8 und insbesondere 3 oder 4 C-Atomen mit Ci-Cis-Alkanolen oder mit Cö-Cs-Cycloalkanolen, insbesondere die Ester der Acrylsäure, der Methacrylsäure, der Crotonsäure, die Diester der Maleinsäure, der Fumarsäure und der Itaconsäure und besonders bevorzugt die Ester der Acrylsäure mit d- bis Cio-Alkanolen (= d- bis - Cio-Alkylacrylate) wie Ethylacrylat, n-Butylacrylat, Isobutylacrylat, tert.-Butylacrylat, n- Hexylacrylat, 2-Ethylhexylacrylat und 3-Propylheptylacrylat und die Ester der Methac- rylsäure mit Ci-bis Cio-Alkanolen wie Ethylmethacrylat, n-Butylmethacrylat, Isobutyl- methacrylat, tert.-Butylmethacrylat, n-Hexylmethacrylat und dergleichen. Geeignete Monomere dieser Art sind außerdem Vinyl- und Allylester gesättigter aliphatischer Car-
bonsäuren mit 1 bis 18 C-Atomen, beispielsweise Vinylacetat, Vinylpropionat sowie die Vinylester der Versatic®-Säuren (Vinylversatate), Vinylhalogenide wie Vinylchlorid und Vinylidenchlorid sowie C2-C6-Olefine wie Ethylen, Propen, 1 -Buten und n-Hexen. Bevorzugte Monomere sind vinylaromatische Monomere, C2-Ci8-Alkylacrylate, insbeson- dere C2-C8-Alkylacrylate, speziell tert.-Butylacrylat sowie C2-Ci8-Alkylmethacrylate und insbesondere C2-C4-Alkylmethacrylate.Examples of main monomers are neutral, monoethylenically unsaturated monomers from the group of vinylaromatic monomers such as styrene, α-methylstyrene, tert-butylstyrene and vinyltoluene, esters of α, β-monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 8 and in particular 3 or 4 C atoms with C 1 -C 6 -alkanols or with C 6 -C 8 -cycloalkanols, in particular the esters of acrylic acid, of methacrylic acid, of crotonic acid, of the diesters of maleic acid, of fumaric acid and of itaconic acid, and particularly preferably of the esters of acrylic acid with C 1 -C 4 -alkenoic acid C 10 -alkanols (= C 1 to C 10 -alkyl acrylates) such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and 3-propylheptyl acrylate and the esters of methacrylic acid with C 1 to C 10 Alkanols such as ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate and the like. Suitable monomers of this type are also vinyl and allyl esters of saturated aliphatic car- carboxylic acids having 1 to 18 carbon atoms, for example vinyl acetate, vinyl propionate and the vinyl esters of Versatic® acids (vinyl versatates), vinyl halides such as vinyl chloride and vinylidene chloride and C 2 -C 6 -olefins such as ethylene, propene, 1-butene and n-hexene. Preferred monomers are vinylaromatic monomers, C 2 -C 18 -alkyl acrylates, in particular C 2 -C 8 -alkyl acrylates, especially tert-butyl acrylate, and C 2 -C 18 -alkyl methacrylates and in particular C 2 -C 4 -alkyl methacrylates.
Insbesondere sind wenigstens 60 Gew.-% der Hauptmonomeren, die bei der Emulsionspolymerisation eingesetzt werden, ausgewählt unter vinylaromatischen Monome- ren, insbesondere Styrol, Estern der Methacrylsäure mit C2-C4-Alkanolen und tert.- Butylacrylat. Besonders bevorzugte Monomere dieser Art sind vinylaromatische Monomere, speziell Styrol, und Mischungen von vinylaromatischen Monomeren mit den vorgenannnten C2-C8-Alkylacrylaten und/oder C2-C4-Alkylmethacrylaten.In particular, at least 60% by weight of the main monomers used in the emulsion polymerization are selected from vinylaromatic monomers, in particular styrene, esters of methacrylic acid with C 2 -C 4 alkanols and tert-butyl acrylate. Particularly preferred monomers of this type are vinyl aromatic monomers, especially styrene, and mixtures of vinyl aromatic monomers with the above-mentioned C2-C8 alkyl acrylates and / or C2-C4 alkyl methacrylates.
Die Monomerzusammensetzung kann außerdem bis zu 20 Gew.-%, bezogen auf das Gesamtgewicht der Monomeren, ein oder mehrere von den Hauptmonomeren (iv) verschiedene monoethylenisch ungesättigte Monomere (v) enthalten. Vorzugsweise macht der Anteil der Monomeren (v) an der Gesamtmenge der Monomeren 15 Gew.- %, insbesondere bis 5 Gew.-% aus. Die Monomeren (v) werden jedoch nur in solchen Mengen eingesetzt, dass die entstehenden Polymeren in Wasser unlöslich sind, so dass man immer Dispersionen erhält.The monomer composition may further contain up to 20% by weight, based on the total weight of the monomers, of one or more monoethylenically unsaturated monomers (v) other than the main monomers (iv). The proportion of monomers (v) in the total amount of monomers is preferably 15% by weight, in particular up to 5% by weight. However, the monomers (v) are used only in amounts such that the resulting polymers are insoluble in water, so that one always receives dispersions.
Zu den Monomeren (v) zählen insbesondere monoethylenisch ungesättigte Monomere, die wenigstens eine Säuregruppe wie eine Sulfonsäure-, eine Phosphonsäure- oder ein oder zwei Carboxylgruppen aufweisen sowie die Salze dieser Monomeren insbesondere die Alkalimetallsalze, z. B. die Natrium- oder Kaliumsalze sowie die Ammoniumsalze. Zu dieser Gruppe von Monomeren (v) zählen ethylenisch ungesättigte SuI- fonsäuren, insbesondere Vinylsulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, 2-Acryloxyethansulfonsäure, 2-Methacryloxyethansulfonsäure, 3-Acryloxy- und 3- Methacryloxypropansulfonsäure, Vinylbenzolsulfonsäure und deren Salze, ethylenisch ungesättigte Phosphonsäuren, wie Vinylphosphonsäure und Vinylphosphonsäuredi- methylester und deren Salze und α,ß-ethylenisch ungesättigte C3-Cs-Mono- und C4-Cs- Dicarbonsäuren, insbesondere Acrylsäure, Methacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure und Itaconsäure. Der Anteil der Säuregruppen aufweisenden Monomere wird häufig nicht mehr als 20 Gew.-%, vorzugsweise nicht mehr als 15 Gew.-%, z. B. 0,1 bis 15 Gew.-% und insbesondere 0,5 bis 10 Gew.-%, bezogen auf die Gesamtmenge der Monomeren, ausmachen.The monomers (v) include in particular monoethylenically unsaturated monomers which have at least one acid group such as a sulfonic acid, a phosphonic acid or one or two carboxyl groups and the salts of these monomers, in particular the alkali metal salts, for. As the sodium or potassium salts and ammonium salts. This group of monomers (v) includes ethylenically unsaturated sulfonic acids, in particular vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloxyethanesulfonic acid, 2-methacryloxyethanesulfonic acid, 3-acryloxy- and 3-methacryloxypropanesulfonic acid, vinylbenzenesulfonic acid and salts thereof, ethylenically unsaturated Phosphonic acids, such as vinylphosphonic acid and vinylphosphonic and methyl esters and their salts and α, ß-ethylenically unsaturated C3-Cs mono- and C 4 -Cs dicarboxylic acids, in particular acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid. The proportion of acid group-containing monomers is often not more than 20 wt .-%, preferably not more than 15 wt .-%, z. B. 0.1 to 15 wt .-% and in particular 0.5 to 10 wt .-%, based on the total amount of the monomers constitute.
Zu den Monomeren der Gruppe (v) zählen weiterhin monoethylenisch ungesättigte, neutrale Monomeren wie die Amide der vorgenannten ethylenisch ungesättigten Carbonsäuren, insbesondere Acrylamid und Methacrylamid, Hydroxyalkylester der vorgenannten α,ß-ethylenisch ungesättigten Cs-Cs-Monocarbonsäuren und der C4-Cs-
Dicarbonsäuren, insbesondere 2-Hydroxyethylacrylat, 2-Hydroxyethylmethacrylat, 2- und 3-Hydroxypropylacrylat, 2- und 3-Hydroxypropylmethacrylat, Ester der vorstehend genannten monoethylenisch ungesättigten Mono- und Dicarbonsäuren mit C2-C4- Polyalkylenglykolen, insbesondere die Ester dieser Carbonsäuren mit Polyethylengly- kol oder Alkyl-Polyethylenglykolen, wobei der (Alkyl)polyethylenglykol-Rest üblicherweise ein Molekulargewicht im Bereich von 100 bis 3000 aufweist. Zu den Monomeren (v) zählen weiterhin N-Vinylamide wie N-Vinylformamid, N-Vinylpyrrolidon, N- Vinylimidazol und N-Vinylcaprolactam. Der Anteil dieser Monomeren wird ebenfalls so gewählt, dass die entstehenden Polymeren in Wasser unlöslich sind. Er beträgt vor- zugsweise nicht mehr als 20 Gew.-%, und insbesondere nicht mehr als 10 Gew.-%, z. B. 0,1 bis 10 und insbesondere 0,5 bis 5 Gew.-%, bezogen auf die Gesamtmenge der Monomeren.The monomers of group (v) also include monoethylenically unsaturated, neutral monomers such as the amides of the abovementioned ethylenically unsaturated carboxylic acids, in particular acrylamide and methacrylamide, hydroxyalkyl esters of the aforementioned α, β-ethylenically unsaturated Cs-Cs monocarboxylic acids and the C 4 -Cs Dicarboxylic acids, in particular 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, 2- and 3-hydroxypropyl methacrylate, esters of the abovementioned monoethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 4 -polyalkylene glycols, in particular the esters of these carboxylic acids with polyethylene glycol or alkyl-polyethylene glycols, wherein the (alkyl) polyethylene glycol radical usually has a molecular weight in the range of 100 to 3000. The monomers (v) also include N-vinylamides such as N-vinylformamide, N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam. The proportion of these monomers is also chosen so that the resulting polymers are insoluble in water. It is preferably not more than 20 wt .-%, and in particular not more than 10 wt .-%, z. B. 0.1 to 10 and in particular 0.5 to 5 wt .-%, based on the total amount of the monomers.
Zu den Monomeren der Gruppe (v) zählen weiterhin monoethylenisch ungesättigte Monomere, die wenigstens eine kationische Gruppe und/oder wenigstens eine im wässrigen Medium protonierbare Aminogruppe, eine quartäre Ammoniumgruppe, eine protonierbare Iminogruppe oder eine quaternisierte Iminogruppe aufweisen. Beispiele für Monomere mit einer protonierbaren Iminogruppe sind N-Vinylimidazol und N- Vinylpyridine. Beispiele für Monomere mit einer quaternisierten Iminogruppe sind N-Alkylvinylpyridiniumsalze und N-Alkyl-N'-vinylimidazoliniumsalze wieMonomers of group (v) furthermore include monoethylenically unsaturated monomers which have at least one cationic group and / or at least one amino group which can be protonated in the aqueous medium, a quaternary ammonium group, a protonatable imino group or a quaternized imino group. Examples of monomers having a protonatable imino group are N-vinylimidazole and N-vinylpyridines. Examples of monomers having a quaternized imino group are N-alkylvinylpyridinium salts and N-alkyl-N'-vinylimidazolinium salts such as
N-Methyl-N'-vinylimidazoliniumchlorid oder Methosulfat. Unter diesen Monomeren werden insbesondere die Monomere der allgemeinen Formel I bevorzugtN-methyl-N'-vinylimidazolinium chloride or methosulfate. Among these monomers, in particular the monomers of general formula I are preferred
worinwherein
R1 Wasserstoff oder Ci-C4-AIkVl, insbesondere Wasserstoff oder Methyl,R 1 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl,
R2, R3 unabhängig voneinander Ci-C4-AIkVl, insbesondere Methyl, undR 2 , R 3 independently of one another Ci-C 4 -AlkVl, in particular methyl, and
R4 Wasserstoff oder Ci-C4-Alkyl, insbesondere Wasserstoff oder Methyl bedeuten,R 4 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl,
Y für Sauerstoff, NH oder NR5 mit R5 = Ci-C4-Alkyl steht,Y is oxygen, NH or NR 5 with R 5 = C 1 -C 4 -alkyl,
A für C2-C8-Alkylen, z. B. 1 ,2-Ethandiyl, 1 ,2- oder 1 ,3-Propandiyl, 1 ,4-Butandiyl oder 2-Methyl-1 ,2-propandiyl, das gegebenenfalls durch 1 , 2 oder 3 nicht benachbarte Sauerstoffatome unterbrochen ist, steht und
X- für ein Anionenäquivalent, z. B. für Ch, HSO4-, ΛA SO4 2" oder CH3OSO3- etc. steht,A is C 2 -C 8 alkylene, e.g. B. 1, 2-ethanediyl, 1, 2- or 1, 3-propanediyl, 1, 4-butanediyl or 2-methyl-1, 2-propanediyl, which is optionally interrupted by 1, 2 or 3 non-adjacent oxygen atoms is and X- for an anion equivalent, e.g. B. for Ch, HSO 4 -, Λ A SO 4 2 " or CH 3 OSO 3 - etc.,
und für Y = H den freien Basen der Monomere der Formel I.and for Y = H, the free bases of the monomers of the formula I.
Beispiele für derartige Monomere sind 2-(N,N-Dimethylamino)ethylacrylat,Examples of such monomers are 2- (N, N-dimethylamino) ethyl acrylate,
2-(N,N-Dimethylamino)ethylmethacrylat, 2-(N,N-Dimethylamino)ethylacrylamid,2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dimethylamino) ethylacrylamide,
3-(N,N-Dimethylamino)propylacrylamid, 3-(N,N-Dimethylamino)propylmethacrylamid,3- (N, N-dimethylamino) propylacrylamide, 3- (N, N-dimethylamino) propylmethacrylamide,
2-(N,N-Dimethylamino)ethylmethacrylamid, 2-(N,N,N-Trimethylammonium)ethylacrylat-Chlorid,2- (N, N-dimethylamino) ethyl methacrylamide, 2- (N, N, N-trimethyl ammonium) ethyl acrylate chloride,
2-(N,N,N-Trimethylammonium)ethylmethacrylat-Chlorid,2- (N, N, N-trimethylammonium) ethyl methacrylate chloride,
2-(N,N,N-Trimethylammonium)ethylmethacrylamid-Chlorid,2- (N, N, N-trimethyl ammonium) ethyl methacrylamide chloride,
3-(N,N,N-Trimethylammonium)propylacrylamid-Chlorid,3- (N, N, N-trimethylammonium) propyl acrylamide chloride,
3-(N,N,N-Trimethylammonium)propylmethacrylamid-Chlorid, 2-(N,N,N-Trimethylammonium)ethylacrylamid-Chlorid, sowie die entsprechenden Me- tosulfate und Sulfate.3- (N, N, N-trimethylammonium) propylmethacrylamide chloride, 2- (N, N, N-trimethylammonium) ethylacrylamide chloride, and the corresponding methosulfates and sulfates.
Der Anteil der kationischen Monomeren beträgt im Emulsionspolymerisat vorteilhafterweise 0,1 bis 20 Gew.-%, insbesondere 0,5 bis 10 Gew.-%, und besonders bevorzugt 1 bis 7 Gew.-%, bezogen auf die Gesamtmenge der Monomeren.The proportion of cationic monomers in the emulsion polymer is advantageously 0.1 to 20 wt .-%, in particular 0.5 to 10 wt .-%, and particularly preferably 1 to 7 wt .-%, based on the total amount of the monomers.
Die Polymeren können gegebenenfalls eine weitere Gruppe von Monomeren (vi) ein- polymerisiert enthalten, die üblicherweise als Vernetzer in einer Emulsionspolymerisation eingesetzt werden können. Der Anteil an Monomeren (vi), die zwei oder mehrere ethylenisch ungesättigte Doppelbindungen aufweisen, macht jedoch üblicherweise nicht mehr als 10 Gew.-%, meistens nicht mehr als 5 Gew.-%, insbesondere nicht mehr als 2 Gew.-%, z. B. 0,01 bis 2 Gew.-% und insbesondere 0,05 bis 1 ,5 Gew.-%, bezogen auf die Gesamtmenge der Monomere aus. Beispiele für Vernetzer sind Bu- tandioldiacrylat, Butandioldimethacrylat, Hexandioldiacrylat, Hexandioldimethacrylat, Glykoldicarylat, Glykoldimethacrylat, Trimethylolpropantriacrylat, Trimethylolpropantri- methyacrylat, Pentaerythrittriacrylat, Pentaerythrittetraacrylat, Diacrylate und Dimethac- rylate von alkoxylierten zweiwertigen Alkoholen, Divinylharnstoff und/oder konjugierte Diolefine wie Butadien oder Isopren.The polymers may optionally contain a further group of monomers (vi) polymerized, which can usually be used as a crosslinker in an emulsion polymerization. The proportion of monomers (vi) having two or more ethylenically unsaturated double bonds, however, usually makes no more than 10 wt .-%, usually not more than 5 wt .-%, in particular not more than 2 wt .-%, z , B. 0.01 to 2 wt .-% and in particular 0.05 to 1, 5 wt .-%, based on the total amount of the monomers. Examples of crosslinkers are butanedioldiacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, glycol dicarylate, glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, diacrylates and dimethacrylates of alkoxylated dihydric alcohols, divinylurea and / or conjugated diolefins such as butadiene or isoprene.
Je nach Anwendungszweck können die Monomeren der Gruppe (vi) auch sogenannte funktionale Monomere umfassen, d.h. Monomere, die neben einer polymerisierbaren C=C-Doppelbindung auch noch eine reaktive funktionelle Gruppe aufweisen, beispielsweise eine Oxirangruppe, eine reaktive Carbonylgruppe, z. B. eine Acetoace- tylgruppe, eine Isocyanat-Gruppe, eine N-Hydroxymethylgruppe, eine N- Alkoxymethylgruppe, eine Trialkylsilylgruppe, eine Trialkoxysilylgruppe oder eine sonstige, gegenüber Nucleophilen reaktive Gruppe.
Von Interesse sind auch solche Emulsionspolymerisate, deren Monomerzusammen- setzung so gewählt ist, dass das resultierende Polymer eine Glasübergangstemperatur von wenigstens 0, vorzugsweise wenigstens 10 0C, insbesondere im Bereich von 20 bis 130 0C aufweist.Depending on the intended use, the monomers of group (vi) may also comprise so-called functional monomers, ie monomers which, in addition to a polymerizable C =C double bond, also have a reactive functional group, for example an oxirane group, a reactive carbonyl group, eg. An acetoacetato group, an isocyanate group, an N-hydroxymethyl group, an N-alkoxymethyl group, a trialkylsilyl group, a trialkoxysilyl group or other nucleophile-reactive group. Also of interest are such emulsion polymers whose Monomerzusammen- reduction is selected so that the resulting polymer has a glass transition temperature of at least 0, preferably at least 10 0 C, in particular in the range of 20 to 130 0 C, respectively.
Um Polymere mit einer solchen Glasübergangstemperatur herzustellen, wählt man beispielsweise die Monomere (i) in der Monomermischung so, dass sie einem Polymerisat 1 mit einer theoretischen Glasübergangstemperatur nach Fox Tg(Fox) von wenigstens 500C entsprechen. Nach Fox (T.G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1 , 123 [1956] und Ullmanns Enzyklopädie der technischen Chemie, Weinheim (1980), S. 17- 18) gilt für die Glasübergangstemperatur von nicht oder schwach vernetzten Mischpolymerisaten bei großen Molmassen in guter NäherungTo prepare polymers having such a glass transition temperature, for example, the monomers (i) are selected in the monomer mixture so that they correspond to a polymer 1 having a theoretical glass transition temperature according to Fox T g (Fox) of at least 50 0 C. According to Fox (TG Fox, Bull. Am. Phys Soc. (Ser. II) 1, 123 [1956] and Ullmann's Encyclopedia of Industrial Chemistry, Weinheim (1980), pp 17-18) applies to the glass transition temperature of not or weakly cross-linked copolymers at high molecular weights in a good approximation
1 X1 X2 X" τα 9 τ g1 τ ' g2 τ ' gn 1 X 1 X 2 X "τ α 9 τ g 1 τ 'g 2 τ' g n
wobei X1, X2, ..., Xn die Massenbrüche der Monomeren 1 , 2, ..., n und T9 1, T9 2, ..., T9" die Glasübergangstemperaturen der jeweils nur aus einem der Monomeren 1 , 2, ..., n aufgebauten Polymeren in Grad Kelvin bedeuten. Letztere sind z. B. aus Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) S. 169 oder aus J. Brandrup, E.H. Immergut, Polymer Handbook 3rd ed., J. Wiley, New York 1989 bekannt.wherein X 1 , X 2 , ..., X n is the mass fractions of the monomers 1, 2, ..., n and T 9 1 , T 9 2 , ..., T 9 "the glass transition temperatures of each of only one of Monomers 1, 2, ..., n of polymers constructed in degrees Kelvin .The latter are, for example, from Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p 169 or from J. Brandrup, EH Immergut, Polymer Handbook 3rd ed., J. Wiley, New York 1989.
Die Polymerisation der Monomeren erfolgt nach der Methode einer Emulsionspolymerisation, d.h. die zu polymerisierenden Monomeren liegen in der Polymerisationsmi- schung als wässrige Emulsion vor. Zum Stabilisieren der Monomeremulsionen verwendet man die gleichen Verbindungen, die als Dispersionsstabilisator zur Herstellung der wässrigen Dispersionen von Reaktivleimungsmitteln verwendet werden, z. B. Ten- side, insbesondere anionische Tenside, wasserlösliche Stärke, vorzugsweise anionische Stärke und Schutzkolloide.The polymerization of the monomers is carried out by the method of emulsion polymerization, i. the monomers to be polymerized are present in the polymerization mixture as an aqueous emulsion. To stabilize the monomer emulsions, use is made of the same compounds which are used as a dispersion stabilizer for the preparation of the aqueous dispersions of reactive sizes, e.g. As surfactants, in particular anionic surfactants, water-soluble starch, preferably anionic starch and protective colloids.
Die Monomeren können im Reaktor vor Beginn der Polymerisation vorgelegt werden oder unter Polymerisationsbedingungen in einer oder mehreren Portionen oder kontinuierlich zu der polymerisierenden Reaktionsmischung zugefügt werden. Beispielsweise kann man die Hauptmenge der Monomeren, insbesondere wenigstens 80% und besonders bevorzugt die Gesamtmenge im Polymerisationsgefäß vorlegen und direkt anschließend die Polymerisation durch Zugabe eines Polymerisationsinitiators starten. Eine weitere Verfahrensvariante besteht darin, dass man zunächst einen Teil (z. B. 5 bis 25 %) der Monomeren oder der Monomeremulsion im Polymerisationsreaktor vorlegt, die Polymerisation durch Zugabe eines Initiators startet und die verbliebene Men- ge an Monomeren bzw. Monomeremulsion dem Reaktor kontinuierlich oder portionsweise zuführt und die Polymerisation der Monomeren zu Ende führt. Der Polymerisati-
onsinitiator kann bei dieser Verfahrensvariante beispielsweise teilweise oder vollständig im Reaktor vorgelegt oder separat von den verbliebenen Monomeren in den Reaktor dosiert werden.The monomers may be initially charged in the reactor prior to the start of the polymerization or added under polymerization conditions in one or more portions or continuously to the polymerizing reaction mixture. For example, you can submit the majority of the monomers, in particular at least 80% and particularly preferably the total amount in the polymerization vessel and then immediately start the polymerization by adding a polymerization initiator. A further process variant consists in initially introducing a part (for example 5 to 25%) of the monomers or the monomer emulsion in the polymerization reactor, starting the polymerization by adding an initiator and the remaining amount of monomers or monomer emulsion to the reactor feeds continuously or in portions and completes the polymerization of the monomers. The polymerisate Onsinitiator can be presented in this process variant, for example, partially or completely in the reactor or metered separately from the remaining monomers in the reactor.
Die für die Emulsionspolymerisation geeigneten Starter sind prinzipiell alle für eine Emulsionspolymerisation geeigneten und üblicherweise verwendeten Polymerisationsinitiatoren, die eine radikalische Polymerisation von ethylenisch ungesättigten Monomeren auslösen. Hierzu zählen beispielsweise Azoverbindungen wie 2,2'-Azobis- isobutyronitril, 2,2'-Azobis(2-methylbutyronitril), 2,2'-Azobis[2-methyl-N-(2- hydroxyethyl)propionamid, 1 ,1 '-Azobis(1-cyclohexancarbonitril), 2,2'-Azobis(2,4- dimethylvaleronitril), 2,2'-Azobis(N,N'-dimethylenisobutyramidin)dihydrochlorid, und 2,2'-Azobis(2-amidinopropan)dihydrochlorid, organische oder anorganische Peroxide wie Diacetylperoxid, Di-tert.-butylperoxid, Diamylperoxid, Dioctano-ylperoxid, Dideca- noylperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(o-toluyl)peroxid, Succinylperoxid, tert.-Butylperacetat, tert.-Butylpermaleinat, tert.-Butylperisobutyrat, tert.-Butylperpivalat, tert.-Butylperoctoat, tert.-Butylperneodecanoat, tert.-Butylperben-zoat, tert- Butylperoxid, tert.-Butylhydroperoxid, Cumolhydroperoxid, tert.-Butylperoxi-2- ethylhexanoat und Diisopropylperoxidicarbamat, Salze der Peroxodischwefelsäure und Redox-I nitiatorsysteme.The starters which are suitable for emulsion polymerization are, in principle, all polymerization initiators which are suitable and usually used for emulsion polymerization and which initiate free-radical polymerization of ethylenically unsaturated monomers. These include, for example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide, 1, 1 '. Azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride, and 2,2'-azobis (2-amidinopropane) dihydrochloride, organic or inorganic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toluyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permaleinate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butylperneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate, salts peroxodisulfuric acid and redox initiator systems.
Vorzugsweise setzt man zur Polymerisation ein Redoxinitiatorsystem ein, insbesondere ein Redoxinitiatorsystem, das als Oxidationsmittel ein Salz der Peroxodischwefelsäure, Wasserstoffperoxid oder ein organisches Peroxid wie tert.-Butylhydroperoxid enthält. Als Reduktionsmittel enthalten die Redoxinitiatorsysteme vorzugsweise eine Schwefelverbindung, die insbesondere ausgewählt ist unter Natriumhydrogensulfit, Natriumhydroxymethansulfinat und dem Hydrogensulfit-Addukt an Aceton. Weitere geeignete Reduktionsmittel sind phosphorhaltige Verbindungen wie phosphorige Säure, Hypophosphite und Phosphinate, sowie Hydrazin bzw. Hydrazinhydrat und Ascor- binsäure. Weiterhin können Redoxinitiatorsysteme einen Zusatz geringer Mengen von Redoxmetallsalzen wie Eisensalze, Vanadiumsalze, Kupfersalze, Chromsalze oder Mangansalze enthalten wie beispielsweise das Redoxinitiatorsystem Ascorbinsäu- re/Eisen(ll)sulfat/Natriumperoxodisulfat. Besonders bevorzugte Redoxinitiatorsysteme sind Acetonbisulfit-Addukt/organisches Hydroperoxid wie tert-Butylhydroperoxid; Natri- umdisulfit (Na2S2θs)/organisches Hydroperoxid wie tert-Butylhydroperoxid; Natrium- hydroxymethansulfinat/organisches Hydroperoxid wie tert-Butylhydroperoxid; und As- corbinsäure/Wasserstoffperoxid.The polymerization is preferably carried out using a redox initiator system, in particular a redox initiator system which contains as oxidizing agent a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide. As the reducing agent, the redox initiator systems preferably contain a sulfur compound, which is especially selected from sodium hydrogen sulfite, sodium hydroxymethanesulfinate and the bisulfite adduct of acetone. Further suitable reducing agents are phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, as well as hydrazine or hydrazine hydrate and ascorbic acid. Furthermore, redox initiator systems may contain an addition of small amounts of redox metal salts, such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate. Particularly preferred redox initiator systems are acetone bisulfite adduct / organic hydroperoxide such as tert-butyl hydroperoxide; Sodium disulfite (Na2S2θs) / organic hydroperoxide such as tert-butyl hydroperoxide; Sodium hydroxymethanesulfinate / organic hydroperoxide such as tert-butyl hydroperoxide; and ascorbic acid / hydrogen peroxide.
Üblicherweise setzt man den Initiator in einer Menge von 0,02 bis 2 Gew.-% und insbesondere 0,05 bis 1 ,5 Gew.-%, bezogen auf die Menge der Monomeren ein. Die op- timale Menge an Initiator hängt naturgemäß von dem eingesetzten Initiatorsystem ab und kann vom Fachmann in Routineexperimenten ermittelt werden. Der Initiator kann teilweise oder vollständig im Reaktionsgefäß vorgelegt werden. Meistens wird ein Teil
der Initiatormenge zusammen mit einem Teil der Monomeremulsion vorgelegt und der restliche Initiator kontinuierlich oder absatzweise zusammen mit den Monomeren, jedoch getrennt davon, zugegeben.The initiator is usually employed in an amount of 0.02 to 2% by weight and in particular 0.05 to 1.5% by weight, based on the amount of the monomers. The optimum amount of initiator naturally depends on the initiator system used and can be determined by the person skilled in the art in routine experiments. The initiator may be partially or completely charged in the reaction vessel. Mostly a part the amount of initiator together with a part of the monomer emulsion and the remaining initiator continuously or batchwise together with the monomers, but separately, added.
Druck und Temperatur sind für die Durchführung der Polymerisation der Monomeren von untergeordneter Bedeutung. Die Temperatur hängt naturgemäß vom eingesetzten Initiatorsystem ab. Die optimale Polymerisationstemperatur kann vom Fachmann mit Hilfe von Routineexperimenten ermittelt werden. Üblicherweise liegt die Polymerisationstemperatur im Bereich von 0 bis 110 0C, häufig im Bereich von 30 bis 95 0C. Die Polymerisation wird üblicherweise bei Normaldruck bzw. Umgebungsdruck durchgeführt. Sie kann aber auch bei erhöhtem Druck, z. B. bis 10 bar oder bei erniedrigtem Druck z. B. bei 20 bis 900 mbar, meistens jedoch bei > 800 mbar durchgeführt werden. Vorzugsweise polymerisiert man unter den sogenannten „starved conditions", d.h. Bedingungen, die möglichst nur eine geringe oder keine Bildung von leeren Mizellen und damit die Bildung von wirkstofffreien Polymerpartikeln erlauben. Hierzu setzt man entweder keine weitere oberflächenaktive Substanz oder nur so wenig weitere oberflächenaktive Substanz zu, so dass die wasserunlöslichen Monomerentröpfchen in der wässrigen Phase stabilisiert werden. So erreicht man, dass keine messbaren Anteile an stabilisierten Tröpfchen von Monomeren in der Reaktionsmischung vorliegen, in denen eine Polymerisation stattfinden kann, und die in der Polymerisationsmischung enthaltenen oberflächenaktiven Substanzen dienen im Wesentlichen zum Netzen der Oberfläche und zum Transport der Monomeren (iv) durch die kontinuierliche wässrige Phase.Pressure and temperature are of minor importance for carrying out the polymerization of the monomers. The temperature naturally depends on the initiator system used. The optimum polymerization temperature can be determined by a person skilled in the art with the aid of routine experiments. Usually, the polymerization temperature is in the range of 0 to 110 0 C, often in the range of 30 to 95 0 C. The polymerization is usually carried out at atmospheric pressure or ambient pressure. But it can also at elevated pressure, z. B. to 10 bar or at reduced pressure z. B. at 20 to 900 mbar, but usually be carried out at> 800 mbar. It is preferred to polymerize under the so-called "starved conditions", ie conditions which permit as little as possible or no formation of empty micelles and thus the formation of active-ingredient-free polymer particles For this purpose, either no further surface-active substance or only very little further surface-active substance is added Thus, it is achieved that there are no measurable levels of stabilized droplets of monomers in the reaction mixture in which polymerization can take place, and the surface active substances contained in the polymerization mixture are used essentially for the purpose of stabilizing the water-insoluble monomer droplets Netting the surface and transporting the monomers (iv) through the continuous aqueous phase.
Falls man bei der Emulsionspolymerisation noch einen Dispersionsstabilisator zum Stabilisieren der entstehenden Emulsionspolymerisate zusetzt, dosiert man vorzugsweise mindestens eine weitere oberflächenaktive Substanz in einer Menge von beispielsweise bis zu 5 Gew.-%, z. B. 0,1 bis 5 Gew.-%, bezogen auf die zu polymerisie- renden Monomeren. Als weitere oberflächenaktive Substanzen kommen neben den nichtionischen oberflächenaktiven Substanzen insbesondere auch anionische Emulga- toren, z. B. Alkylsulfate, Alkylsulfonate, Alkylarylsulfonate, Alkylethersulfate, Alkylary- lethersulfate, anionische Stärke, Sulfosuccinate wie Sulfobernsteinsäurehalbester und Sulfobernsteinsäurediester und Alkyletherphosphate sowie weiterhin kationische E- mulgatoren in Betracht. Diese Verbindungen werden bei der Herstellung der Kompo- nente (a) der erfindungsgemäßen Mischungen als Tenside eingesetzt.If, in emulsion polymerization, a dispersion stabilizer is added to stabilize the resulting emulsion polymers, it is preferable to add at least one further surface-active substance in an amount of, for example, up to 5% by weight, e.g. B. 0.1 to 5 wt .-%, based on the monomer to be polymerized monomers. As a further surface-active substances in addition to the nonionic surface-active substances in particular also anionic emulsifiers, z. As alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alkyl ether sulfates, alkylaryl ether sulfates, anionic starch, sulfosuccinates such as sulfosuccinic monoesters and sulfosuccinic and alkyl ether and further cationic E- emulsifiers into consideration. These compounds are used as surfactants in the preparation of the component (a) of the mixtures according to the invention.
In einer bevorzugten Ausführungsform der Erfindung führt man die Emulsionspolymerisation der Monomeren in Gegenwart von beispielsweise bis zu 20 Gew.-%, meistens bis 10 Gew.-%, bezogen auf die gesamte Dispersion, einer kationisch oder anionisch modifizierten Stärke durch.
Natürlich kann man der Reaktionsmischung, die polymerisiert werden soll, weitere Zusatzstoffe beifügen, die in der Emulsionspolymerisation üblich sind, beispielsweise Glykole, Polyethylenglykole, Puffer/pH-Wert-Regulatoren, Molekulargewichtsregler und Kettenübertragungsinhibitoren.In a preferred embodiment of the invention, the emulsion polymerization of the monomers is carried out in the presence of, for example, up to 20% by weight, usually up to 10% by weight, based on the total dispersion, of a cationically or anionically modified starch. Of course, one can add to the reaction mixture to be polymerized, other additives that are common in emulsion polymerization, for example, glycols, polyethylene glycols, buffer / pH regulators, molecular weight regulators and chain transfer inhibitors.
Um die Eigenschaften der Polymeren zu modifizieren, kann man die Emulsionspolymerisation gegebenenfalls in Gegenwart mindestens eines Polymerisationsreglers durchführen. Beispiele für Polymerisationsregler sind organische Verbindungen, die Schwefel in gebundener Form enthalten wie Dodecylmercaptan, Thiodiglykol, Ethylthioetha- nol, Di-n-butylsulfid, Di-n-octylsulfid, Diphenylsulfid, Diisopropyldisulfid, 2- Mercaptoethanol, 1 ,3-Mercaptopropanol, 3-Mercaptopropan-1 ,2-diol, 1 ,4- Mercaptobutanol, Thioglykolsäure, 3-Mercaptopropionsäure, Mercaptobernsteinsäure, Thioessigsäure und Thioharnstoff, Aldehyde wie Formaldehyd, Acetaldehyd und Propi- onaldehyd, organische Säuren wie Ameisensäure, Natriumformiat oder Ammonium- formiat, Alkohole wie insbesondere Isopropanol sowie Phosphorverbindungen wie Natriumhypophosphit. Falls man bei der Polymerisation einen Regler einsetzt, so beträgt die jeweils verwendete Menge beispielsweise 0,01 bis 5, vorzugsweise 0,1 bis 1 Gew.-%, bezogen auf die bei der Polymerisation eingesetzten Monomeren. Polymerisationsregler und Vernetzer können bei der Polymerisation gemeinsam eingesetzt werden. Damit kann man beispielsweise die Rheologie der entstehenden Polymerdispersionen steuern.In order to modify the properties of the polymers, the emulsion polymerization can optionally be carried out in the presence of at least one polymerization regulator. Examples of polymerization regulators are organic compounds which contain sulfur in bound form, such as dodecylmercaptan, thiodiglycol, ethylthioethanol, di-n-butylsulfide, di-n-octylsulfide, diphenyl sulfide, diisopropyl disulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, 3 Mercaptopropan-1, 2-diol, 1, 4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioacetic acid and thiourea, aldehydes such as formaldehyde, acetaldehyde and propionaldehyde, organic acids such as formic acid, sodium formate or ammonium formate, alcohols such as in particular Isopropanol and phosphorus compounds such as sodium hypophosphite. If one uses a regulator in the polymerization, the amount used in each case, for example, 0.01 to 5, preferably 0.1 to 1 wt .-%, based on the monomers used in the polymerization. Polymerization regulators and crosslinkers can be used together in the polymerization. This can be used, for example, to control the rheology of the resulting polymer dispersions.
Die Polymerisation wird in der Regel bei pH-Werten von 2 bis 9, vorzugsweise im schwach sauren Bereich bei pH-Werten von 3 bis 5,5 durchgeführt. Der pH-Wert kann vor oder während der Polymerisation mit üblichen Säuren wie Salzsäure, Schwefelsäure oder Essigsäure oder auch mit Basen wie Natronlauge, Kalilauge, Ammoniak, Am- moniumcarbonat, usw. auf den gewünschten Wert eingestellt werden. Bevorzugt wird die Dispersion nach Beendigung der Polymerisation mit Natronlauge, Kalilauge oder Ammoniak auf einen pH-Wert zwischen 5 und 7 eingestellt.The polymerization is generally carried out at pH values of 2 to 9, preferably in the weakly acidic range at pH values of 3 to 5.5. The pH can be adjusted to the desired value before or during the polymerization with customary acids such as hydrochloric acid, sulfuric acid or acetic acid or else with bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia, ammonium carbonate, etc. After the polymerization has ended, the dispersion is preferably adjusted to a pH of between 5 and 7 using sodium hydroxide solution, potassium hydroxide solution or ammonia.
Um die restlichen Monomeren möglichst weitgehend aus der Polymerdispersion zu entfernen, führt man nach Abschluss der eigentlichen Polymerisation zweckmäßigerweise eine Nachpolymerisation durch. Hierfür setzt man der Polymerdispersion nach Beendigung der Hauptpolymerisation beispielsweise einen Initiator aus der Gruppe Wasserstoffperoxid, Peroxide, Hydroperoxide und/oder Azostarter zu. Die Kombination der Initiatoren mit geeigneten Reduktionsmitteln, wie beispielsweise Ascorbinsäure oder Natriumbisulfit, ist ebenfalls möglich. Bevorzugt werden öllösliche, in Wasser schwerlösliche Initiatoren verwendet, z. B. übliche organische Peroxide wie Dibenzoyl- peroxid, Di-tert.-Butylperoxid, tert.-Butylhydroperoxid, Cumylhydroperoxid oder Bis- cyclohexylperoxidicarbonat eingesetzt. Zur Nachpolymerisation wird das Reaktionsgemisch beispielsweise auf eine Temperatur erhitzt, die der Temperatur entspricht, bei der die Hauptpolymerisation durchgeführt wurde oder die um bis zu 200C, vorzugswei-
se bis zu 100C höher liegt. Die Hauptpolymerisation ist beendet, wenn der Polymerisationsinitiator verbraucht ist bzw. der Monomerumsatz beispielsweise mindestens 98%, vorzugsweise mindestens 99,5 % beträgt. Zur Nachpolymerisation wird vorzugsweise tert.-Butylhydroperoxid eingesetzt. Die Polymerisation wird beispielsweise in einem Temperaturbereich von 40 bis 1000C, meistens 50 bis 95°C durchgeführt.In order to remove the remaining monomers as far as possible from the polymer dispersion, a postpolymerization is expediently carried out after completion of the actual polymerization. For this purpose, the polymer dispersion after completion of the main polymerization, for example, an initiator from the group of hydrogen peroxide, peroxides, hydroperoxides and / or azo starters. The combination of the initiators with suitable reducing agents, such as ascorbic acid or sodium bisulfite, is also possible. Preferably oil-soluble, sparingly soluble in water initiators are used, for. As customary organic peroxides such as dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide or bis-cyclohexylperoxidicarbonat used. For postpolymerization, the reaction mixture is heated, for example, to a temperature which corresponds to the temperature at which the main polymerization has been carried out or which may be up to 20 ° C., preferably se is up to 10 0 C higher. The main polymerization is complete when the polymerization initiator is consumed or the monomer conversion is, for example, at least 98%, preferably at least 99.5%. For postpolymerization tert-butyl hydroperoxide is preferably used. The polymerization is carried out for example in a temperature range of 40 to 100 0 C, usually 50 to 95 ° C.
Nach Beendigung der Polymerisation kann man einen Komplexbildner für Schwermetallionen in einer solchen Menge zur Polymerdispersion zusetzen, dass sämtliche Schwermetallionen komplex gebunden sind. Die stärkehaltigen Polymerdispersionen enthalten dispergierte Teilchen mit einer mittleren Teilchengröße von beispielsweise 20 bis 500 nm, vorzugsweise 50 bis 250 nm. Die mittlere Teilchengröße kann durch dem Fachmann bekannte Methoden wie beispielsweise Laserkorrelationsspektroskopie, Ultrazentrifugation oder CHDF (Capillary Hydodynamic Fractionation) bestimmt werden. Ein weiteres Maß für die Teilchengröße der dispergierten Polymerteilchen ist der LD-Wert (Wert für die Lichtdurchlässigkeit). Zur Bestimmung des LD-Wertes wird die jeweils zu untersuchende Polymerdispersion in 0,1 gew.-%iger wässriger Verdünnung in einer Küvette mit einer Kantenlänge von 2,5 cm mit Licht der Wellenlänge 600 nm vermessen und mit der entsprechenden Durchlässigkeit von Wasser unter den gleichen Messbedingungen verglichen. Die Durchlässigkeit von Wasser wird dabei mit 100 % angegeben. Je feinteiliger die Dispersion ist, desto höher ist der LD-Wert, der nach der zuvor beschriebenen Methode gemessen wird. Aus den Messwerten kann die mittlere Teilchengröße errechnet werden, vgl. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prag, 1976, Edice Marco, Rada D- DATA, SVAZEK D-1.After the polymerization has ended, a complexing agent for heavy metal ions can be added to the polymer dispersion in an amount such that all heavy metal ions are complexed. The starch-containing polymer dispersions contain dispersed particles having an average particle size of, for example, 20 to 500 nm, preferably 50 to 250 nm. The mean particle size can be determined by methods known to the person skilled in the art, such as, for example, laser correlation spectroscopy, ultracentrifugation or CHDF (Capillary Hydodynamic Fractionation). Another measure of the particle size of the dispersed polymer particles is the LD (translucency) value. To determine the LD value, the particular polymer dispersion to be examined is measured in 0.1% by weight aqueous dilution in a cuvette with an edge length of 2.5 cm with light of wavelength 600 nm and with the appropriate permeability of water under the same measurement conditions compared. The permeability of water is given as 100%. The finer the dispersion, the higher the LD value measured by the method described above. The average particle size can be calculated from the measured values, cf. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prague, 1976, Edice Marco, Rada D-DATA, SVAZEK D-1.
Der Feststoffgehalt der stärkehaltigen Polymerdispersion beträgt beispielsweise 5 bis 50 Gew.-%, und liegt vorzugsweise in dem Bereich von 15 bis 40 Gew.-%.The solids content of the starch-containing polymer dispersion is, for example, 5 to 50% by weight, and is preferably in the range of 15 to 40% by weight.
Die erfindungsgemäßen Papierleimungsmittelmischungen enthalten beispielsweise als Komponente (b) ein Emulsionspolymerisat ausThe paper size mixtures according to the invention comprise, for example, as component (b) an emulsion polymer
(iv) mindestens einem Alkylacrylat, Alkylmethacrylat, Vinylester von 1 bis 20 C-(iv) at least one alkyl acrylate, alkyl methacrylate, vinyl ester of 1 to 20 C
Atome aufweisenden gesättigten Carbonsäuren, Vinylaromaten mit bis zu 20 C- Atomen, ethylenisch ungesättigten Nitril, Vinylhalogenid, Vinylether von 1 bis 10Atoms having saturated carboxylic acids, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitrile, vinyl halide, vinyl ethers of 1 to 10
C-Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoff mit 2 bis 8 C-Atomen und ein oder zwei Doppelbindungen undC-containing alcohols, aliphatic hydrocarbon having 2 to 8 carbon atoms and one or two double bonds and
(v) gegebenenfalls mindestens einem kationischen und/oder mindestens einem anionischen Monomeren.
In einer bevorzugten Ausführungsform besteht die Komponente (b) aus einem Emulsionspolymerisat aus(v) optionally at least one cationic and / or at least one anionic monomer. In a preferred embodiment, component (b) consists of an emulsion polymer
(iv) einem Alkylacrylat, Alkylmethacrylat, Styrol, Acrylnitril, Methacrylnitril und deren Mischungen und(iv) an alkyl acrylate, alkyl methacrylate, styrene, acrylonitrile, methacrylonitrile and mixtures thereof and
(v) einem Dialkylaminoalkylacrylat, Dialkylaminoalkylmethacrylat, Diallyldimethy- lammoniumchlorid, Dialkylaminoalkylacrylamid, Dialkylaminoalkylmethacrylamid, Acrylsäure, Methacrylsäure, Itakonsäure, Maleinsäure, Fumarsäure, Crotonsäure sowie deren Mischungen.(v) a dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, diallyldimethylammonium chloride, dialkylaminoalkylacrylamide, dialkylaminoalkylmethacrylamide, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and mixtures thereof.
enthalten.contain.
Als Komponente (b) wird in einer besonders bevorzugten Ausführungsform eine wäss- rige Dispersion eines Emulsionspolymerisats eingesetzt, das durch Polymerisieren von ethylenisch ungesättigten Monomeren in Gegenwart einer abgebauten Stärke erhältlich ist. Solche Emulsionspolymerisate sind ebenfalls bekannt. Sie werden beispielsweise als Leimungsmittel für Papier verwendet, vgl. JP-A 58/1 15 196, EP-B 0 257 412, EP-B 0 267 770, EP-A 0 307 812, EP-A 0 536 597, EP-A 1 056 783, WO 00/23479, WO 02/14393, EP-B 1 165 642 und WO 2004/078807.Component (b) used in a particularly preferred embodiment is an aqueous dispersion of an emulsion polymer obtainable by polymerizing ethylenically unsaturated monomers in the presence of a degraded starch. Such emulsion polymers are also known. They are used, for example, as a sizing agent for paper, cf. JP-A 58/1 15 196, EP-B 0 257 412, EP-B 0 267 770, EP-A 0 307 812, EP-A 0 536 597, EP-A 1 056 783, WO 00/23479, WO 02/14393, EP-B 1 165 642 and WO 2004/078807.
Von besonderem technischen Interesse sind dabei Emulsionspolymerisate, die durch Polymerisieren vonOf particular technical interest are emulsion polymers obtained by polymerizing
(iv) Acrylnitril, Methacrylnitril, Styrol und/oder C4- bis C24-Olefinen und (v) Ethylacrylat, n-Butylacrylat, tert.-Butylacrylat, Hexylacrylat und/oder Ethylhexylac- rylat und gegebenenfalls (vi) weiteren Monomeren(iv) acrylonitrile, methacrylonitrile, styrene and / or C 4 to C 24 olefins and (v) ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, hexyl acrylate and / or ethylhexyl acrylate and optionally (vi) other monomers
in einer wässrigen Lösung einer abgebauten Stärke erhältlich sind. Als Stärke eignen sich sämtliche native Stärken wie Kartoffelstärke, Maisstärke, Weizenstärke, Reisstärke, Stärken mit einem Amylopektingehalt von mehr als 95% und Tapiokastärke sowie kationisch und anionisch modifizierte Stärken. Die Stärken werden einem Molgewichtsabbau unterworfen, bevor man die Polymerisation in der Lösung einer abgebauten Stärke durchführt. Der Abbau der Stärke kann oxydativ, hydrolytisch oder enzymatisch vorgenommen werden. Vorzugsweise baut man die Stärke enzymatisch ab. Die Molmassen Mw der abgebauten Stärken liegen beispielsweise in dem Bereich von 1000 bis 100 000, vorzugsweise 1000 bis 60 000. Die Polymerdispersionen können beispielweise bis zu 20 Gew.-% mindestens einer abgebauten Stärke enthalten. Meistens beträgt der Gehalt an abgebauter Stärke in den als Komponente (b) verwendeten Emulsions- polymerisaten 5 bis 15 Gew.-%.
Außerdem kommen als Komponente (b) wässrige Dispersionen in Betracht, die durch radikalische Polymerisation von Monomeren der obengenannten Gruppen (iv) und (v) in Gegenwart von niedrigmolekularen Vorpolymerisaten als Emulgator erhältlich sind. Solche Vorpolymerisate sind beispielsweise aus der EP-A 0 051 144 bekannt. Sie wer- den durch eine zweistufige Polymerisation hergestellt, wobei man in der ersten Polymerisationsstufe eine Monomermischung, die pro Mol eines stickstoffhaltigen Monomeren, das eine Amino- und/oder quaternäre Ammoniumgruppe trägt, 2,5 bis 10 Mol mindestens eines nichtionischen, hydrophoben, ethylenisch ungesättigten Monomeren, 0,5 bis 1 ,5 Mol einer ethylenisch ungesättigten Carbonsäure und gegebenenfalls bis 9 Mol eines nichtionischen, hydrophilen, ethylenisch ungesättigten Monomeren enthält in einem mit Wasser mischbaren Lösemittel nach Art einer Lösungscopolymerisation po- lymerisiert, dann die Lösung des Vorpolymerisats mit Wasser verdünnt und darin ethylenisch ungesättigte Monomere nach Art einer Emulsionspolymerisation polymerisiert. Als Lösemittel für die Herstellung der Vorpolymerisate kommen beispielsweise Car- bonsäuren wie Ameisensäure, Essigsäure und Propionsäure, Alkohole wie Methanol, Ethanol, n-Propanol oder Isopropanol und Ketone wie Aceton oder Methylethylketon sowie Dimethylformamid in Betracht. Um beispielweise ein als Komponente (b) der Papierleimungsmittelmischungen geeignetes Emulsionspolymerisat herzustellen, kann man die oben beschriebenen Monomeren (iv) und (v) sowie gegebenenfalls (vi) nach Art einer Emulsionspolymerisation in einer wässrigen Lösung eines solchen Vorpolymerisats polymerisieren.in an aqueous solution of degraded starch. Suitable starches are all native starches such as potato starch, corn starch, wheat starch, rice starch, starches with an amylopectin content of more than 95% and tapioca starch and cationically and anionically modified starches. The starches are subjected to molecular weight degradation before polymerization is carried out in the solution of degraded starch. The breakdown of the starch can be carried out oxidatively, hydrolytically or enzymatically. Preferably, the starch is enzymatically degraded. The molecular weights M w of the degraded starches are, for example, in the range from 1000 to 100 000, preferably from 1000 to 60 000. The polymer dispersions may contain, for example, up to 20% by weight of at least one degraded starch. In most cases, the content of degraded starch in the emulsion polymers used as component (b) is 5 to 15% by weight. Also suitable as component (b) are aqueous dispersions obtainable by free-radical polymerization of monomers of the abovementioned groups (iv) and (v) in the presence of low molecular weight prepolymers as emulsifier. Such prepolymers are known, for example, from EP-A 0 051 144. They are prepared by a two-stage polymerization, wherein in the first polymerization stage, a monomer mixture containing from 2.5 to 10 moles of at least one nonionic, hydrophobic, ethylenic, per mole of a nitrogen-containing monomer carrying an amino and / or quaternary ammonium group unsaturated monomers, 0.5 to 1, 5 moles of an ethylenically unsaturated carboxylic acid and optionally up to 9 moles of a nonionic, hydrophilic, ethylenically unsaturated monomer polymerized in a water-miscible solvent in the manner of a solution copolymerization, then the solution of the prepolymer with water diluted and polymerized therein ethylenically unsaturated monomers in the manner of emulsion polymerization. Suitable solvents for the preparation of the prepolymers are, for example, carboxylic acids such as formic acid, acetic acid and propionic acid, alcohols such as methanol, ethanol, n-propanol or isopropanol and ketones such as acetone or methyl ethyl ketone and also dimethylformamide. For example, to prepare an emulsion polymer suitable as component (b) of the paper size-compound mixtures, the above-described monomers (iv) and (v) and optionally (vi) may be polymerized in an aqueous solution of such a prepolymer in the manner of emulsion polymerization.
Die erfindungsgemäßen Papierleimungsmittelmischungen können z. B. als Komponente (b) eine wässrige Dispersionen eines Emulsionspolymerisates enthalten, das durch radikalische Polymerisation vonThe paper size mixtures according to the invention can, for. Example, as component (b) an aqueous dispersions of an emulsion polymer containing by radical polymerization of
(iv) mindestens einem Alkylacrylat, Alkylmethacrylat, Vinylester von 1 bis 20 C-(iv) at least one alkyl acrylate, alkyl methacrylate, vinyl ester of 1 to 20 C
Atome aufweisenden gesättigten Carbonsäuren, Vinylaromaten mit bis zu 20 C- Atomen, ethylenisch ungesättigten Nitril, Vinylhalogenid, Vinylether von 1 bis 10 C-Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoff mit 2 bis 8Atoms having saturated carboxylic acids, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitrile, vinyl halide, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbon having 2 to 8
C-Atomen und ein oder zwei Doppelbindungen undC atoms and one or two double bonds and
(v) gegebenenfalls mindestens einem kationischen und/oder mindestens einem anionischen Monomeren(v) optionally at least one cationic and / or at least one anionic monomer
in Gegenwart mindestens eines niedrigmolekularen Vorpolymerisats als Emulgator erhältlich ist.in the presence of at least one low molecular weight prepolymer is available as an emulsifier.
Ein weiteres Beispiel für Polymerisate, die als Komponente (b) der erfindungsgemäßen Mischungen in Betracht kommen, sind Emulsionspolymerisate, die erhältlich sind durch radikalische Polymerisation von
(iv) 30 bis 60 Gew.-% mindestens eines gegebenenfalls substituierten Styrols, Ac- rylnitril und/oder Methacrylnitril (v) 5 bis 50 Gew.-% mindestens eines Acrylsäure-d-C-^-alkylesters und/oder eines Methacrylsäure-d-C-^-alkylesters, (vi) 5 bis 30 Gew.-% mindestens eines C4- bis C24-Olefins,A further example of polymers which are suitable as component (b) of the mixtures according to the invention are emulsion polymers obtainable by free-radical polymerization of (iv) from 30 to 60% by weight of at least one optionally substituted styrene, acrylonitrile and / or methacrylonitrile (v) from 5 to 50% by weight of at least one acrylic acid C 1 -C 4 -alkyl ester and / or of a methacrylic acid C 1 -C 4 (iii) from 5 to 30% by weight of at least one C 4 to C 24 olefin,
(vii) 0 bis 10 Gew.-% mindestens eines anderen ethylenisch ungesättigten copoly- merisierbaren Monomers, und (viii) 15 bis 35 Gew.-% einer abgebauten Stärke,(vii) 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer, and (viii) 15 to 35% by weight of a degraded starch,
wobei die Summe (iv) + (v) + (vi) + (vii) + (viii) = 100% beträgt und sich auf den Gesamtfeststoffgehalt bezieht. Für die Herstellung dieser Polymerdispersionen setzt man als Olefine vorzugsweise Isobuten, Diisobuten, Octen-1 , Decen-1 , Dodecen-1 sowie Mischungen solcher Olefine ein.where the sum (iv) + (v) + (vi) + (vii) + (viii) = 100% and refers to the total solids content. Isobutene, diisobutene, octene-1, decene-1, dodecene-1 and mixtures of such olefins are preferably used as olefins for the preparation of these polymer dispersions.
Die Papierleimungsmittelmischungen können darüber hinaus als Komponente (b) auch mindestens ein nicht dispergierend wirkendes wasserlösliches oder in Wasser disper- gierbares Polymerisat aus der Gruppe der Ethylenimineinheiten enthaltenden Polymeren, wasserlöslichen Polyurethane, wasserlöslichen Polyester, wasserlöslichen Ethy- lencopolymerisate mit anionischen und/oder kationischen Monomeren oder deren Mi- schungen enthalten. Die Molmassen Mw dieser Polymerisate betragen beispielsweise mindestens 5 000, vorzugsweise mindestens 100 000. Sie liegen meistens in dem Bereich von 50 000 bis 500 000.In addition, the paper size mixtures may also contain as component (b) at least one non-dispersible water-soluble or water-dispersible polymer from the group of polymers containing ethyleneimine units, water-soluble polyurethanes, water-soluble polyesters, water-soluble ethylene copolymers with anionic and / or cationic monomers or containing their mixtures. The molecular weights M w of these polymers are for example at least 5,000, preferably at least 100,000. They are usually in the range from 50,000 to 500,000.
Ethylenimineinheiten enthaltende Polymere sind bekannt. Sie werden beispielsweise durch Polymerisieren von Ethylenimin in wässrigem Medium in Gegenwart von z. B. Säuren, halogenierten Kohlenwasserstoffen oder Lewis-Säuren als Katalysator hergestellt. Sie sind außerdem durch Pfropfen von Ethylenimin auf basische Stickstoffatome enthaltende Verbindungen zugänglich, z. B. durch Pfropfen von Kondensaten aus einem Polyamidoamin und einer Dicarbonsäure mit Ethylenimin, vgl. DE-B 24 34 816. Ein handelübliches Produkt dieser Art ist Polymin® SK von BASF, Ludwigshafen.Ethylenimine units containing polymers are known. They are, for example, by polymerizing ethyleneimine in an aqueous medium in the presence of z. As acids, halogenated hydrocarbons or Lewis acids as a catalyst. They are also accessible by grafting of ethyleneimine compounds containing basic nitrogen atoms, for. B. by grafting condensates of a polyamidoamine and a dicarboxylic acid with ethyleneimine, cf. DE-B 24 34 816. A commercially available product of this kind is Polymin® SK from BASF, Ludwigshafen.
Vinylamineinheiten enthaltende Polymere sind durch Hydrolyse von Vinylformamidein- heiten enthaltenden Polymeren erhältlich. Polyvinylamine werden beispielsweise durch Hydrolyse von Homopolymeren des N-Vinylformamids hergestellt, wobei der Hydroly- segrad beispielsweise bis zu 100%, meistens 70 bis 95% beträgt. Auch hochmolekulare Copolymerisate von N-Vinylformamid mit anderen ethylenisch ungesättigten Monomeren wie Vinylacetat, Vinylpropionat, Acrylsäuremethylester, Methacrylsäuremethy- lester, Acrylamid, Acrylnitril und/oder Methacrylnitril, können zu Vinylamineinheiten enthaltenden Polymeren hydrolysiert und erfindungsgemäß als Komponente (b) einge- setzt werden. Die Vinylamineinheiten enthaltenden Polymeren sind kationisch. Bei der Hydrolyse von Polymeren des N-Vinylformamids mit Säuren entstehen die Salze der Polymeren (Ammoniumsalze), während bei der Hydrolyse mit Basen wie Natronlauge
oder Kalilauge Aminogruppen tragende Polymere entstehen. Die Herstellung von Homo- und Copolymerisaten von N-Vinylformamid und die Herstellung der daraus durch Hydrolyse erhältlichen Amino- bzw. Ammoniumgruppen aufweisenden Polymeren ist bekannt. Sie wird beispielsweise in der US 6,132,558, Spalte 2 Zeile 36 bis Spalte 5, Zeile 25 ausführlich beschrieben. Die dort gemachten Ausführungen werden hiermit durch Bezugnahme zum Offenbarungsgehalt der vorliegenden Anmeldung gemacht.Vinylamine-containing polymers are obtainable by hydrolysis of vinylformamide units containing polymers. Polyvinylamines are prepared, for example, by hydrolysis of homopolymers of N-vinylformamide, the degree of hydrolysis being, for example, up to 100%, usually 70 to 95%. High molecular weight copolymers of N-vinylformamide with other ethylenically unsaturated monomers such as vinyl acetate, vinyl propionate, methyl acrylate, Methacrylsäuremethy- ester, acrylamide, acrylonitrile and / or methacrylonitrile, can be hydrolyzed to Vinylamineinheiten containing polymers and according to the invention as component (b) sets. The polymers containing vinylamine units are cationic. In the hydrolysis of polymers of N-vinylformamide with acids, the salts of the polymers (ammonium salts), while in the hydrolysis with bases such as sodium hydroxide or potassium hydroxide amino groups bearing polymers arise. The preparation of homo- and copolymers of N-vinylformamide and the preparation of the polymers obtainable therefrom by hydrolysis of amino or ammonium groups is known. It is described in detail in, for example, US Pat. No. 6,132,558, column 2, line 36 to column 5, line 25. The statements made there are hereby incorporated by reference into the disclosure content of the present application.
Als Komponente (b) der erfindungsgemäßen Mischungen eignen sich außerdem jeweils nicht dispergierend wirkende, modifizierte Polyamine, die mit Ethylenimin ge- pfropft und gegebenenfalls vernetzt sind, Polyetheramide, Polyvinylimidazole, Polyvi- nylpyrrolidine, Polyvinylimidazoline, Polyvinyltetrahydropyrine, Po- ly(dialkylaminoalkylvinylether) sowie Poly(dialkylaminoalkyl(meth)acrylate) in protonier- ter oder in quaternierter Form.Also suitable as component (b) of the mixtures according to the invention are non-dispersing, modified polyamines grafted with ethyleneimine and optionally crosslinked, polyetheramides, polyvinylimidazoles, polyvinylpyrrolidines, polyvinylimidazolines, polyvinyltetrahydropyrines, poly (dialkylaminoalkylvinyl ethers) and also poly (Dialkylaminoalkyl (meth) acrylates) in protonated or in quaternized form.
Die oben beschriebenen feinteiligen, wässrigen Mischungen aus (a) einer Dispersion eines Reaktivleimungsmittels und (b) einem Emulsionspolymerisat und/oder einem nicht dispergierend wirkenden wasserlöslichen Polymer werden als Leimungsmittel für Papier und Papierprodukte wie Pappe und Karton verwendet. Sie können sowohl als Oberflächenleimungsmittel als auch als Masseleimungsmittel in den jeweils üblichen Mengen eingesetzt werden. Bevorzugt ist die Anwendung als Oberflächenleimungsmittel. Dabei können die erfindungsgemäßen Mischungen der Dispersionen aus den Komponenten (a) und (b) mit allen bei der Oberflächenleimung geeigneten Verfahrensmethoden verarbeitet werden. Für die Anwendung wird die Dispersion üblicherweise der Leimpressenflotte in einer Menge von 0,05 bis 5 Gew.-%, bezogen auf Fest- Substanz, zugesetzt und richtet sich nach dem gewünschten Leimungsgrad der auszurüstenden Papiere oder Papierprodukte. Des weiteren kann die Leimpressenflotte weitere Stoffe enthalten, wie z. B. Stärke, Pigmente, optische Aufheller, Biozide, Verfestiger für Papier, Fixiermittel, Entschäumer, Retentionsmittel, und/oder Entwässerungsmittel. Die Leimungsmitteldispersion kann auf Papier, Pappe oder Karton mittels einer Leimpresse oder anderen Auftragsaggregaten wie Filmpresse, Speedsizer oder Gateroll aufgebracht werden. Die Menge an Polymer, die so auf die Oberfläche von Papierprodukten aufgetragen wird, beträgt beispielsweise 0,005 bis 1 ,0 g/m2, vorzugsweise 0,01 bis 0,5 g/m2.The finely divided, aqueous mixtures of (a) a dispersion of a reactive sizing agent described above and (b) an emulsion polymer and / or a non-dispersing water-soluble polymer are used as sizing agents for paper and paper products such as cardboard and paperboard. They can be used both as surface sizing agents and as engine size agents in the customary amounts. Preferably, the application is as a surface sizing agent. In this case, the novel mixtures of the dispersions of components (a) and (b) can be processed with all process methods suitable for surface sizing. For the application, the dispersion is usually added to the size press liquor in an amount of 0.05 to 5% by weight, based on solid substance, and depends on the desired degree of sizing of the papers or paper products to be finished. Furthermore, the size press fleet may contain other substances such. As starch, pigments, optical brighteners, biocides, solidifiers for paper, fixing agents, defoamers, retention aids, and / or dehydrating agents. The sizing agent dispersion can be applied to paper, cardboard or cardboard by means of a size press or other application units such as a film press, Speedsizer or Gateroll. The amount of polymer thus applied to the surface of paper products is, for example, 0.005 to 1.0 g / m 2 , preferably 0.01 to 0.5 g / m 2 .
Die erfindungsgemäßen Papierleimungsmittelmischungen können zur Herstellung sämtlicher Papiersorten verwendet werden, z. B. von Schreib- und Druckpapieren sowie Verpackungspapieren, insbesondere von Papieren für die Verpackung von Flüssigkeiten.The paper sizes mixtures according to the invention can be used for the production of all types of paper, for. As of writing and printing papers and packaging papers, in particular of papers for the packaging of liquids.
Papierprodukte, die mit den erfindungsgemäßen, feinteiligen, stärkehaltigen Polymerdispersionen geleimt sind, haben gegenüber Papieren, die mit bekannten Leimungs-
mittein geleimt sind, einen verbesserten Leimungsgrad, eine gute Sofortleimung, eine verbesserte Ink-Jet-Bedruckbarkeit und eine gute Tonerhaftung.Paper products glued with the fine-particle, starch-containing polymer dispersions according to the invention have, compared with papers which are known with known sizing agents. with improved sizing, good instant sizing, improved ink-jet printability, and good toner adhesion.
Sofern aus dem Zusammenhang nichts anderes hervorgeht, bedeuten die Prozentan- gaben in den Beispielen immer Gewichtsprozent, die Teile sind Gewichtsteile. Die Teilchengrößen wurden mittels eines High Performance Particle Sizer (HPPS) der Fa. Malvern unter Verwendung eines He-Ne-Lasers (633 nm) bei einem Streuwinkel von 173° bestimmt.Unless otherwise stated in the context, the percentages in the examples always mean percent by weight, the parts are parts by weight. The particle sizes were determined using a High Performance Particle Sizer (HPPS) from Malvern using a He-Ne laser (633 nm) at a scattering angle of 173 °.
BeispieleExamples
Herstellung von wässrigen AlkylketendimerdispersionenPreparation of aqueous Alkylketendimerdispersionen
AKD-Dispersion AAKD dispersion A
120 g Stearyldiketen, 871 ,3 g vollständig entsalztes Wasser, 12 g Natriumdocecylsul- fonat und 7,6 g eines Kondensationsprodukts aus Naphthalinsulfonsäure und Formaldehyd (Tamol® NNP) wurden gemischt und auf eine Temperatur von 85°C erhitzt. Sobald diese Temperatur erreicht war, wurde die Mischung mit Hilfe eines UltraTurrax® Gerätes bei 6000 UpM innerhalb von 5 Minuten voremulgiert und anschließend bei 800C dreimal mit einem Homogenisator (AVP Gaulin LAB 40, 600 bar) emulgiert und schnell auf Raumtemperatur abgekühlt. Man erhielt eine feinteilige wässrige Dispersion von Stearyldiketen mit einer mittleren Teilchengrößenverteilung von 144 nm.Sulfonate 120 g stearyidiketene, 871, 3 g of demineralized water, 12 g Natriumdocecylsul- and 7.6 g of a condensation product of naphthalenesulfonic acid and formaldehyde (Tamol ® NNP) were mixed and heated to a temperature of 85 ° C. Once this temperature was reached, the mixture was pre-emulsified with the aid of an Ultraturrax ® apparatus at 6000 rpm over 5 minutes and then at 80 0 C three times with a homogenizer (AVP Gaulin LAB 40, 600 bar) emulsified and rapidly cooled to room temperature. A finely divided aqueous dispersion of stearyl diketene having an average particle size distribution of 144 nm was obtained.
AKD-Dispersion BAKD dispersion B
120 g Stearydiketen, 871 ,3 g vollständig entsalztes Wasser, 8,2 g eines 10fach ethoxy- lierten Ci3-Oxoalkohols und 7,6 g eines Kondensationsproduktes aus Naphthalinsulfonsäure und Formaldehyd (Tamol® NNP) wurden gemischt und auf eine Temperatur von 85°C erhitzt. Bei dieser Temperatur wurde die Mischung mit einem UltraTurrax® bei 6000 UpM 5 Minuten voremulgiert. Danach emulgierte man die Mischung bei 800C dreimal mit einem homogenisator (APV Gaulin LAB 40, 600 bar) und kühlte die Emulsion schnell auf Raumtemperatur ab. Man erhielt eine feinteilige wässrige Dispersion von Stearydiketen mit einer mittleren Teilchengrößenverteilung von 167 nm.120 g stearyldiketene, 871, 3 g of demineralized water, 8.2 g of a 10X Ci3 ethoxylated oxo alcohol and 7.6 g of a condensation product of naphthalenesulfonic acid and formaldehyde (Tamol ® NNP) were mixed and heated to a temperature of 85 ° C heated. At this temperature the mixture with a UltraTurrax® ® at 6000 rpm was pre-emulsified for 5 minutes. Thereafter, the mixture was emulsified three times at 80 ° C. with a homogenizer (APV Gaulin LAB 40, 600 bar) and the emulsion was rapidly cooled to room temperature. A finely divided aqueous dispersion of stearydiketene having an average particle size distribution of 167 nm was obtained.
AKD-Dispersion CAKD dispersion C
120 g Stearydiketen, 871 ,3 g vollständig entsalztes Wasser, 10,4g eines Oleylami- nethoxylates (Lipamin® OK) und 34,5 g einer Maltodextrinstärke (mittlere Molmasse Mw ca. 10.000 da) wurden gemischt und auf eine Temperatur von 85°C erhitzt. Nachdem diese Temperatur erreicht war, wurde die Mischung mit einem UltraTurrax® bei 6000 UpM 5 Minuten voremulgiert, danach bei einer Temperatur von 800C dreimal mit
einem Homogenisator (APV Gaulin LAB 40, 600 bar) emulgiert und schnell auf Raumtemperatur abgekühlt. Man erhielt eine feinteilige wässrige Dispersion von Stearyldike- ten mit einer mittleren Teilchengröße von 185 nm.120 g stearyldiketene, 871, 3 g of demineralized water, 10.4 g of a Oleylami- nethoxylates (Lipamin ® OK) and 34.5 g of a maltodextrin starch (average molecular weight Mw about 10,000 Da) were mixed and heated to a temperature of 85 ° C heated. After this temperature was reached, the mixture with a UltraTurrax® ® at 6000 rpm was pre-emulsified for 5 minutes then at a temperature of 80 0 C three times with emulsified in a homogenizer (APV Gaulin LAB 40, 600 bar) and cooled rapidly to room temperature. This gave a finely divided aqueous dispersion of Stearyldike- th with an average particle size of 185 nm.
Beispiele 1 - 6Examples 1 - 6
In einem mit einem Rührer ausgestatteten 1 ,5I Rührgefäß mischte man bei einer Drehzahl des Rührers von 250 UpM und einer Temperatur von 25°C die oben beschriebenen AKD-Dispersionen A - C mit den in den folgenden Beispielen jeweils angegebe- nen Polymeren, wobei man die Polymeren zu der im Kolben vorgelegten AKD-In a 1, 5I stirred vessel equipped with a stirrer, the above-described AKD dispersions A - C were mixed at a speed of the stirrer of 250 rpm and a temperature of 25 ° C with the polymers respectively indicated in the following examples, wherein the polymers to the AKD presented in the piston
Dispersion innerhalb von 15 Minuten dosierte. Die Mischungen wurden anschließend als Oberflächen- und Masseleimungsmittel für Papier geprüft.Dispersion metered within 15 minutes. The blends were then tested as surface and sizing agents for paper.
Beispiel 1example 1
Mischen von 30 Teilen AKD-Dispersion A mit 70 Teilen einer 24,9.%igen wässrigen Dispersion eines in Gegenwart von anionischer Stärke hergestellten Copolymerisates aus Styrol und Butylacrylat (Basoplast® 400 DS).Mixing 30 parts of AKD dispersion A with 70 parts of a 24.9.% Aqueous dispersion of a copolymer produced in the presence of anionic starch of styrene and butyl acrylate (Basoplast ® 400 DS).
Beispiel 2Example 2
Mischen von 30 Teilen AKD-Dispersion A mit 70 Teilen einer 35,4.%igen wässrigen Dispersion eines in Gegenwart von anionischer Stärke hergestellten Copolymerisates aus Styrol und Butylacrylat (Basoplast® PR 8152).Mixing 30 parts of AKD dispersion A with 70 parts of a 35.4.% Aqueous dispersion of a copolymer produced in the presence of anionic starch of styrene and butyl acrylate (Basoplast ® PR 8152).
Beispiel 3Example 3
Mischen von 30 Teilen AKD-Dispersion C mit 70 Teilen einer 30,3%igen wässrigen Dispersion eines Copolymerisates, das in einer wässrigen Lösung eines kationischen Vorpolymerisates durch Polymerisieren von Styrol und Butylacrylat erhältlich ist (Basoplast® 270 D).Mixing 30 parts of AKD dispersion C with 70 parts of a 30.3% aqueous dispersion of a copolymer which is obtainable in an aqueous solution of a cationic prepolymer by polymerizing styrene and butyl acrylate (Basoplast ® 270 D).
Beispiel 4Example 4
Mischen von 40 Teilen AKD-Dispersion B mit 60 Teilen einer 20 %igen wässrigen Lösung eines zu 10 % hydrolysierten Polyvinylformamids (Copolymerisat enthaltend 90 mol% Vinylformamideinheiten und 10 mol% Vinylamineinheiten) (Lupamin® 9010).
Beispiel 5Mixing 40 parts of AKD dispersion B with 60 parts of a 20% aqueous solution of a 10% hydrolyzed polyvinylformamide (copolymer containing 90 mol% of vinylformamide units and 10 mol% of vinylamine units) (Lupamin ® 9010). Example 5
Mischen von 30 Teilen AKD-Dispersion C mit 70 Teilen einer 34,8 %igen wässrigen Dispersion eines in Gegenwart von kationischer Stärke hergestellten Copolymerisates aus Acrylnitril und Butylacrylat (Basoplast® PR 250).Mixing 30 parts of AKD dispersion C with 70 parts of a 34.8% aqueous dispersion of a copolymer prepared in the presence of cationic starch of acrylonitrile and butyl acrylate (Basoplast ® PR 250).
Beispiel 6Example 6
Mischen von 30 Teilen AKD-Dispersion A mit 70 Teilen einer 30,1 %igen wässrigen Dispersion eines in Gegenwart von anionischer Stärke hergestellten Copolymerisates aus Acrylnitril und Butylacrylat (Basoplast® PR 335).Mixing 30 parts of AKD dispersion A with 70 parts of a 30.1% aqueous dispersion of a copolymer produced in the presence of anionic starch acrylonitrile and butyl acrylate (Basoplast ® PR 335).
PrüfmethodenTest Methods
Die Bestimmung des Leimungsgrades erfolgte nach CobbθO gemäß DIN EN 20 535. Der HST-Wert wurde nach dem Hercules Sizing Test gemäß Tappi Norm T 530 ermittelt. Die Tintenschwimmzeit wurde gemäß DIN 53 126 mit einer Papierprüftinte blau durchgeführt. Die Tonerhaftung wurde mit einem IGT-Tester gemäß der Vorschrift EN 12 283 durchgeführt.The determination of the degree of sizing was carried out according to CobbθO according to DIN EN 20 535. The HST value was determined according to the Hercules Sizing Test in accordance with Tappi Standard T 530. The Inkschwimmzeit was carried out according to DIN 53 126 with a Papierprüfinte blue. The toner adhesion was carried out with an IGT tester according to the regulation EN 12 283.
Anwendungstechnische Prüfungen:Application tests:
1 ) Anwendungstechnische Prüfung als Oberflächenleimungsmittel für holzfreie Papiere1) Application testing as a surface sizing agent for woodfree papers
Eine anionisch modifizierte Kartoffelstärke wurde unter Erhitzen auf 95 0C für 30 Minuten in Lösung gebracht. Anschließend wurde die Stärkelösung mit der zu prüfenden Polymerdispersion versetzt, und mit Wasser verdünnt, sodass in der fertigen Mischung eine Stärkekonzentration von 8 % vorlag. Die Mischung aus Stärkelösung und Polymerdispersion wurde anschließend mittels einer Leimpresse auf ein holzfreies, unge- leimtes Papier mit einer Grammatur von 80 g/m2 bei einer Temperatur von 55 0C aufgetragen. Die Präparationsaufnahme lag im Bereich von 50 - 60 %. Anschließend wurden die so behandelten Papiere mittels Kontakttrocknung bei 90 0C getrocknet, 24 h bei 50 % Luftfeuchte klimatisiert und dann den oben angegebenen Prüfungen unterzogen.An anionically modified potato starch was dissolved by heating at 95 ° C. for 30 minutes. Subsequently, the starch solution was added to the polymer dispersion to be tested, and diluted with water, so that in the finished mixture, a starch concentration of 8% was present. The mixture of starch solution and the polymer dispersion was then coated by means of a size press on a wood-free, unsized paper with a grammage of 80 g / m 2 at a temperature of 55 0 C. The preparation uptake was in the range of 50-60%. Subsequently, the papers thus treated were dried by means of contact drying at 90 0 C, air-conditioned for 24 h at 50% humidity and then subjected to the tests indicated above.
Zum Vergleich mit dem Stand der Technik wurden folgende Zusammensetzungen geprüft:
Vergleichsbeispiel 1For comparison with the prior art, the following compositions were tested: Comparative Example 1
Handelsübliche wässrige Leimungsmitteldispersion (Basoplast® 400DS) auf Basis eines Styrol/Butylacrylat-Polymerisates. Der Feststoffgehalt der Dispersion betrug 24,9 %, die Teilchengrößenverteilung 101 nm.Commercially available aqueous dispersion of sizing agents (Basoplast ® 400DS) based on a styrene / butyl acrylate polymer. The solids content of the dispersion was 24.9%, the particle size distribution 101 nm.
Vergleichsbeispiel 2Comparative Example 2
Handelsübliche Stearyldiketendispersion, mittlere Teilchengröße des dispergierten Stearyldiketens 980nmCommercial Stearyldiketendispersion, average particle size of the dispersed Stearyldiketens 980nm
Vergleichsbeispiel 3: AKD-Dispersion AComparative Example 3: AKD dispersion A
Vergleichsbeispiel 4: AKD-Dispersion BComparative Example 4: AKD Dispersion B
Vergleichsbeispiel 5: AKD-Dispersion CComparative Example 5: AKD dispersion C
Die bei den Prüfungen für die Oberflächenleimung erhaltenen Ergebnisse sind in Tabelle 1 angegeben.The results obtained in the surface sizing tests are shown in Table 1.
Tabelle 1Table 1
2) Anwendungstechnische Prüfung als Oberflächenleimungsmittel für Testliner2) Application testing as a surface sizing agent for testliner
Eine native Maisstärke wurde unter Erhitzen auf 95 0C für 30 Minuten in Lösung gebracht und durch Zugabe von alpha-Amylase auf einen Viskosität von ca. 30mPas (Brookfield, Spindel 1 , 50 0C) abgebaut. Anschließend wurde die Stärkelösung jeweils
mit den zu prüfenden Dispersionen (i.e. Leimungsmittel aus den Beispielen 1-6 bzw. Vergleichsbeispielen 1-5) versetzt, und mit Wasser verdünnt, sodass in der fertigen Mischung eine Stärkekonzentration von 8 % vorlag. Die Mischung aus Stärkelösung und Leimungsmitteldispersion wurde anschließend mittels einer Leimpresse auf einen Testliner (100 % Altpapier, 100 g/m2) bei einer Temperatur von 55 0C aufgetragen. Die Präparationsaufnahme lag im Bereich von ca. 65 %. Anschließend wurden die so behandelten Papiere mittels Kontakttrocknung bei 90 0C getrocknet, 24 h bei 50 % Luftfeuchte klimatisiert und dann den oben angegebenen Prüfungen unterzogen. Die Ergebnisse sind in Tabelle 2 angegeben. (Konzentration Leimungsmittel in der MischungA native corn starch was brought into solution with heating to 95 0 C for 30 minutes and degraded by the addition of alpha-amylase to a viscosity of about 30mPas (Brookfield, spindle 1, 50 0 C). Subsequently, the starch solution each with the dispersions to be tested (ie, sizing agent from Examples 1-6 and Comparative Examples 1-5), and diluted with water, so that in the finished mixture, a starch concentration of 8% was present. The mixture of starch solution and size dispersion was then applied to a test liner by means of a size press (100% recycled paper, 100 g / m 2) at a temperature of 55 0 C. The preparation uptake was in the range of approximately 65%. Subsequently, the papers thus treated were dried by means of contact drying at 90 0 C, air-conditioned for 24 h at 50% humidity and then subjected to the tests indicated above. The results are shown in Table 2. (Concentrate sizing agent in the mixture
1 g/i)1 g / i)
Tabelle 2Table 2
3) Anwendungstechnische Prüfung als Masseleimungsmittel3) Application testing as engine size agent
Zu einem Papierstoff mit einer Stoffdichte von 8 g/l aus einer vollständig gebleichten Mischung von 70 % Kiefern- und 30 % Birkensulfatzellstoff mit einem Mahlgrad von 35 0SR (Schopper-Riegler) gab man, jeweils bezogen auf trockenes Fasergemisch, jeweils 1 ,2 kg/t, immer bezogen auf den Feststoffgehalt, an Leimungsmittelmischung (Beispiele 1-6) bzw. Leimungsmittel (Vergleichsbeispiele 1-5) sowie 20 % Calciumcarbonat, 0,6 % einer kationischen Massestärke und 0,04 % eines kationischen Polyacrylamids (Polymin® KE215) als Retentionsmittel. Der pH-Wert der Papierslurry wurde auf 7 eingestellt. Die Papierstoffe wurden jeweils auf einem Rapid-Köthen-Blattbildner zu einem Blatt mit einem Flächengewicht von 80 g/m2 verarbeitet. Danach wurden dieTo a pulp with a consistency of 8 g / l of a fully bleached mixture of 70% pine and 30% birch sulphate pulp with a freeness of 35 0 SR (Schopper-Riegler) was given, each based on dry fiber mixture, each 1, 2 kg / t, based on the solids content, sizing agent mixture (Examples 1-6) or sizing agents (Comparative Examples 1-5) and 20% calcium carbonate, 0.6% of a cationic starch and 0.04% of a cationic polyacrylamide (Polymin ® KE215) as retention agent. The pH of the paper slurry was adjusted to 7. The stocks were each processed on a Rapid-Kothen sheet former into a sheet having a basis weight of 80 g / m 2 . After that, the
Blätter auf einem mit Dampf beheizten Trockenzylinder bei einer Temperatur von 900C auf einen Wassergehalt von 5 % getrocknet, anschließend 24 Stunden bei 25 0C und einer relativen Luftfeuchtigkeit von 50 % gelagert und dann die Werte für Cobb 60 und die Tintenschwimmdauer bestimmt. Die Messwerte sind in Tabelle 3 angegeben.
Tabelle 3Leaves are dried on a steam-heated drying cylinder at a temperature of 90 0 C to a water content of 5%, then stored for 24 hours at 25 0 C and a relative humidity of 50% and then determines the values for Cobb 60 and the ink buoyancy. The measured values are given in Table 3. Table 3
Claims
1. Papierleimungsmittelmischungen aus einem in Wasser dispergierten Reaktivlei- mungsmittel und einem Polymeren, dadurch gekennzeichnet, dass sie erhältlich sind durch Mischen von1. Paper size mixtures of a water-dispersed reactive lubricant and a polymer, characterized in that they are obtainable by mixing
(a) einer wässrigen Dispersion eines Reaktivleimungsmittels, dessen disper- gierte Teilchen einen mittleren Teilchendurchmesser von weniger als 500 nm aufweisen, wobei die Dispersion durch Emulgieren mindestens eines Reaktivleimungsmittels in Wasser in Gegenwart mindestens eines Ten- sids erhältlich ist, und(A) an aqueous dispersion of a reactive sizing agent whose dispersed particles have a mean particle diameter of less than 500 nm, wherein the dispersion is obtainable by emulsifying at least one reactive sizing agent in water in the presence of at least one surfactant, and
(b) mindestens eines Emulsionspolymerisates und/oder mindestens eines gegenüber Reaktivleimungsmitteln nicht dispergierend wirkenden, wasserlöslichen Polymers und/oder eines in Wasser dispergierbaren PoIy- mers.(b) at least one emulsion polymer and / or at least one water-soluble polymer which does not disperse against reactive sizing agents and / or a water-dispersible polymer.
2. Papierleimungsmittelmischungen nach Anspruch 1 , dadurch gekennzeichnet, dass die Komponente (a) der Mischungen eine wässrige Dispersion eines Reaktivleimungsmittels ist, dessen dispergierte Teilchen einen mittleren Teilchen- durchmesser von höchstens 300 nm haben.2. Paper size mixtures according to claim 1, characterized in that component (a) of the mixtures is an aqueous dispersion of a reactive sizing agent whose dispersed particles have an average particle diameter of at most 300 nm.
3. Papierleimungsmittelmischungen nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Komponente (a) der Mischungen als Reaktivleimungsmittel eine wässrige Dispersion eines Alkylketendimeren und/oder eines Alkenyl- bernsteinsäureanhydrids mit einer mittleren Teilchengröße der dispergierten3. paper size mixtures according to claim 1 or 2, characterized in that the component (a) of the mixtures as a reactive sizing agent, an aqueous dispersion of an alkyl ketene dimer and / or an alkenylsuccinic anhydride having an average particle size of the dispersed
Teilchen von 30 bis 300 nm enthält.Contains particles of 30 to 300 nm.
4. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Gewichtsverhältnis der Komponenten (a) und (b) in der Mischung 1 : 100 bis 100 : 1 beträgt.4. Paper size mixtures according to one of claims 1 to 3, characterized in that the weight ratio of components (a) and (b) in the mixture is 1: 100 to 100: 1.
5. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Gewichtsverhältnis der Komponenten (a) und (b) in der Mischung 1 : 20 bis 20 : 1 beträgt.5. Paper size mixtures according to one of claims 1 to 4, characterized in that the weight ratio of components (a) and (b) in the mixture is 1: 20 to 20: 1.
6. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass sie als Komponente6. Papierleimungsmittelmischungen according to one of claims 1 to 5, characterized in that they as a component
(a) eine wässrige Dispersion eines Alkylketendimeren enthalten, das mit Hilfe eines kationischen, anionischen und/oder nichtionischen Tensids emul- giert ist, und als Komponente (b) mindestens ein Emulsionspolymerisat mit einem mittleren Teilchendurchmesser von höchsten 1000 nm enthalten.(A) an aqueous dispersion of an alkyl ketene dimer which is emulsified with the aid of a cationic, anionic and / or nonionic surfactant, and as a component (B) at least one emulsion polymer having a mean particle diameter of 1000 nm highest included.
7. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Komponente (a) der Mischungen erhältlich ist durch7. Paper size mixtures according to one of claims 1 to 6, characterized in that the component (a) of the mixtures is obtainable by
Emulgieren eines Reaktivleimungsmittels in Gegenwart eines Tensids und mindestens eines Dispergiermittels und/oder mindestens eines Schutzkolloids.Emulsifying a reactive sizing agent in the presence of a surfactant and at least one dispersant and / or at least one protective colloid.
8. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Komponente (a) der Mischungen erhältlich ist durch8. paper size mixtures according to one of claims 1 to 7, characterized in that the component (a) of the mixtures is obtainable by
Emulgieren eines Reaktivleimungsmittels in Gegenwart eines Tensids und mindestens eines Schutzkolloids aus der Gruppe der Polyvinylalkohole, Polyvinyl- pyrrolidone, Polyacrylsäuren, Polyalkylenglykole, ein- oder beidseitig mit Alkyl-, Carboxyl- oder Aminogruppen endgruppenverschlossenen Polyalkylenglykole, Polydiallyldimethylammoniumchloride, wasserlöslichen Stärken, wasserlöslichenEmulsifying a reactive sizing agent in the presence of a surfactant and at least one protective colloid from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acids, polyalkylene glycols, on one or both sides with alkyl, carboxyl or amino end-capped polyalkylene glycols, polydiallyldimethylammonium chlorides, water-soluble starches, water-soluble
Stärkederivate und/oder wasserlöslichen Proteine.Starch derivatives and / or water-soluble proteins.
9. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Komponente (a) der Mischungen erhältlich ist durch Emulgieren eines Reaktivleimungsmittels in Gegenwart eines Tensids und mindestens eines Dispergiermittels aus der Gruppe der Kondensate aus Naphtha- linsulfonsäure und/oder deren Salzen und Formaldehyd, Ligninsulfonsäure und/oder deren Salzen, amphiphilen Polymere und/oder Nanopartikeln aus organischen Polymeren oder aus anorganischen Verbindungen.9. Paper size mixtures according to one of claims 1 to 7, characterized in that component (a) of the mixtures is obtainable by emulsifying a reactive sizing agent in the presence of a surfactant and at least one dispersant from the group of condensates of naphthalenesulfonic acid and / or salts thereof and formaldehyde, lignosulfonic acid and / or salts thereof, amphiphilic polymers and / or nanoparticles of organic polymers or of inorganic compounds.
10. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Komponente (a) der Mischungen erhältlich ist durch Emulgieren eines Reaktivleimungsmittels in Gegenwart eines anionischen Tensids und mindestens eines Dispergiermittels aus einem Kondensat aus Naphtha- linsulfonsäure und Formaldehyd und gegebenenfalls mindestens eines Schutzkolloids.10. Paper size mixtures according to any one of claims 1 to 9, characterized in that the component (a) of the mixtures is obtainable by emulsifying a reactive sizing agent in the presence of an anionic surfactant and at least one dispersant from a condensate of naphthaleninsulfonic acid and formaldehyde and optionally at least one protective colloid.
1 1. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass sie als Komponente (b) eine wässrige Dispersion eines Emulsionspolymerisats aus mindestens einem ethylenisch ungesättigten Monomeren enthalten.11. Paper blends according to claim 1, characterized in that they contain as component (b) an aqueous dispersion of an emulsion polymer of at least one ethylenically unsaturated monomer.
12. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass sie als Komponente (b) ein Emulsionspolymerisat aus12. Paper size mixtures according to one of claims 1 to 11, characterized in that it comprises as component (b) an emulsion polymer
(iv) mindestens einem Alkylacrylat, Alkylmethacrylat, Vinylester von 1 bis 20 C-Atome aufweisenden gesättigten Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitril, Vinylhalogenid, Vinyl- ether von 1 bis 10 C-Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoff mit 2 bis 8 C-Atomen und ein oder zwei Doppelbindungen und (v) gegebenenfalls von mindestens einem kationischen und/oder mindestens einem anionischen Monomeren enthalten.(iv) at least one alkyl acrylate, alkyl methacrylate, vinyl esters of saturated carboxylic acids having from 1 to 20 carbon atoms, vinylaromatics having bis to 20 carbon atoms, ethylenically unsaturated nitrile, vinyl halide, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds and (v) optionally of at least one cationic and / or or at least one anionic monomer.
13. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass sie als Komponente (b) ein Emulsionspolymerisat aus13. paper size mixtures according to any one of claims 1 to 12, characterized in that it comprises as component (b) an emulsion polymer
(iv) einem Alkylacrylat, Alkylmethacrylat, Styrol, Acrylnitril, Methacrylnitril und deren Mischungen und(iv) an alkyl acrylate, alkyl methacrylate, styrene, acrylonitrile, methacrylonitrile and mixtures thereof and
(v) einem Dialkylaminoalkylacrylat, Dialkylaminoalkylmethacrylat, Diallyldi- methylammoniumchlorid, Dialkylaminoalkylacrylamid, Dialkylaminoalkyl- methacrylamid, Acrylsäure, Methacrylsäure, Itakonsäure, Maleinsäure, Fumarsäure, Crotonsäure sowie deren Mischungen enthalten.(v) a dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, diallyldimethylammonium chloride, dialkylaminoalkylacrylamide, dialkylaminoalkyl methacrylamide, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and mixtures thereof.
14. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass sie als Komponente (b) eine wässrige Dispersion eines Emulsionspolymerisats enthalten, das durch Polymerisieren von ethylenisch ungesättigten Monomeren in Gegenwart einer abgebauten Stärke erhältlich ist.14. Blending paper mixtures according to any one of claims 1 to 12, characterized in that they contain as component (b) an aqueous dispersion of an emulsion polymer which is obtainable by polymerizing ethylenically unsaturated monomers in the presence of a degraded starch.
15. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass sie als Kommponente (b) eine wässrige Dispersion eines Emulsionspolymerisates enthalten, das durch radikalische Polymerisation von15. Paper size mixtures according to one of claims 1 to 12, characterized in that they contain as component (b) an aqueous dispersion of an emulsion polymer which is obtained by free-radical polymerization of
(iv) mindestens einem Alkylacrylat, Alkylmethacrylat, Vinylester von 1 bis 20 C-Atome aufweisenden gesättigten Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitril, Vinylhalogenid, Vinyl- ether von 1 bis 10 C-Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoff mit 2 bis 8 C-Atomen und ein oder zwei Doppelbindungen und (v) gegebenenfalls mindestens einem kationischen und/oder mindestens einem anionischen Monomeren(iv) at least one alkyl acrylate, alkyl methacrylate, vinyl esters of saturated carboxylic acids having from 1 to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitrile, vinyl halide, vinyl ethers of alcohols containing from 1 to 10 carbon atoms, aliphatic Hydrocarbon having 2 to 8 carbon atoms and one or two double bonds and (v) optionally at least one cationic and / or at least one anionic monomer
in Gegenwart mindestens eines niedrigmolekularen Vorpolymerisats als Emulga- tor erhältlich ist.in the presence of at least one low molecular weight prepolymer is available as emulsifier.
16. Papierleimungsmittelmischungen nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass sie als Komponente (b) mindestens ein nicht dispergie- rend wirkendes wasserlösliches oder in Wasser dispergierbares Polymerisat aus der Gruppe der Ethylenimineinheiten enthaltenden Polymeren, Vinylamineinhei- ten enthaltenden Polymerisate, Polyurethane, Polyester, Ethylencopolymerisa- te mit anionischen und/oder kationischen Monomeren oder deren Mischungen enthalten.16. Paper size mixtures according to one of claims 1 to 15, characterized in that they contain at least one non-dispersible component (b) rend acting water-soluble or water-dispersible polymer from the group of ethyleneimine units containing polymers containing vinylamine polymers, polyurethanes, polyesters, ethylene copolymers with anionic and / or cationic monomers or mixtures thereof.
17. Verwendung der Papierleimungsmittelmischungen nach den Ansprüchen 1 bis 16 zur Masse- und Oberflächenleimung von Papier und Papierprodukten. 17. Use of the Papierleimungsmittelmischungen according to claims 1 to 16 for the mass and surface sizing of paper and paper products.
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2007
- 2007-12-11 JP JP2009541979A patent/JP2010513734A/en active Pending
- 2007-12-11 EP EP07848052A patent/EP2126209A1/en not_active Withdrawn
- 2007-12-11 CN CN200780047555XA patent/CN101568687B/en not_active Expired - Fee Related
- 2007-12-11 WO PCT/EP2007/063681 patent/WO2008074690A1/en active Application Filing
- 2007-12-11 US US12/518,312 patent/US20100016478A1/en not_active Abandoned
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2014
- 2014-07-31 JP JP2014156352A patent/JP2014208942A/en not_active Withdrawn
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104294708A (en) * | 2013-09-30 | 2015-01-21 | 昆山市巴城镇顺拓工程机械配件厂 | Styrene-acrylic emulsion surface sizing agent |
Also Published As
Publication number | Publication date |
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JP2014208942A (en) | 2014-11-06 |
US20100016478A1 (en) | 2010-01-21 |
CN101568687B (en) | 2012-06-27 |
JP2010513734A (en) | 2010-04-30 |
CN101568687A (en) | 2009-10-28 |
WO2008074690A1 (en) | 2008-06-26 |
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