EP1743018B1 - Copolymers comprising n-heterocyclic groups, and use thereof as an additive in detergents - Google Patents
Copolymers comprising n-heterocyclic groups, and use thereof as an additive in detergents Download PDFInfo
- Publication number
- EP1743018B1 EP1743018B1 EP05734132A EP05734132A EP1743018B1 EP 1743018 B1 EP1743018 B1 EP 1743018B1 EP 05734132 A EP05734132 A EP 05734132A EP 05734132 A EP05734132 A EP 05734132A EP 1743018 B1 EP1743018 B1 EP 1743018B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomer
- copolymer
- monomers
- mol
- alkylene oxide
- 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.)
- Not-in-force
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 79
- 239000003599 detergent Substances 0.000 title description 59
- 239000000654 additive Substances 0.000 title description 4
- 230000000996 additive effect Effects 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 120
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 238000009472 formulation Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 9
- 239000013042 solid detergent Substances 0.000 claims abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 3
- -1 allyl ethers Chemical class 0.000 claims description 79
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 36
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 25
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- 150000002148 esters Chemical group 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical class C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 29
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 22
- 238000012546 transfer Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 18
- 239000007844 bleaching agent Substances 0.000 description 17
- 239000000975 dye Substances 0.000 description 16
- 239000003112 inhibitor Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 11
- 108090000790 Enzymes Proteins 0.000 description 10
- 102000004190 Enzymes Human genes 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- 229940088598 enzyme Drugs 0.000 description 10
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 10
- 239000011976 maleic acid Substances 0.000 description 10
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 150000003951 lactams Chemical class 0.000 description 6
- 150000004760 silicates Chemical class 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 4
- XHULUQRDNLRXPF-UHFFFAOYSA-N 3-ethenyl-1,3-oxazolidin-2-id-4-one Chemical compound C(=C)N1[CH-]OCC1=O XHULUQRDNLRXPF-UHFFFAOYSA-N 0.000 description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical class C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 125000006413 ring segment Chemical group 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- XWRBMHSLXKNRJX-UHFFFAOYSA-N 2-ethenyl-1-oxidopyridin-1-ium Chemical class [O-][N+]1=CC=CC=C1C=C XWRBMHSLXKNRJX-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 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 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000005956 quaternization reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 2
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 2
- UBPXWZDJZFZKGH-UHFFFAOYSA-N 1-ethenyl-3-methylpyrrolidin-2-one Chemical compound CC1CCN(C=C)C1=O UBPXWZDJZFZKGH-UHFFFAOYSA-N 0.000 description 2
- RYAFIHABDOQVHL-UHFFFAOYSA-N 1-ethenyl-4-methylazepan-2-one Chemical compound CC1CCCN(C=C)C(=O)C1 RYAFIHABDOQVHL-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
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- FOFGHOIKFUUAPZ-UHFFFAOYSA-N 3-ethenyl-5-methyl-1,3-oxazolidin-2-id-4-one Chemical compound C(=C)N1[CH-]OC(C1=O)C FOFGHOIKFUUAPZ-UHFFFAOYSA-N 0.000 description 2
- KRFXUBMJBAXOOZ-UHFFFAOYSA-N 4-ethenyl-1-oxidopyridin-1-ium Chemical class [O-][N+]1=CC=C(C=C)C=C1 KRFXUBMJBAXOOZ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- JWOWFSLPFNWGEM-UHFFFAOYSA-N Cl.Cl.NC(=N)C(C)CN=NCC(C)C(N)=N Chemical compound Cl.Cl.NC(=N)C(C)CN=NCC(C)C(N)=N JWOWFSLPFNWGEM-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 229920002266 Pluriol® Polymers 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- 239000012669 liquid formulation Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- JFZUABNDWZQLIJ-UHFFFAOYSA-N methyl 2-[(2-chloroacetyl)amino]benzoate Chemical compound COC(=O)C1=CC=CC=C1NC(=O)CCl JFZUABNDWZQLIJ-UHFFFAOYSA-N 0.000 description 1
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- 239000001923 methylcellulose Substances 0.000 description 1
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- BBJPLYGBSPMDOU-UHFFFAOYSA-N n-[acetyl(methyl)carbamoyl]-n-methylacetamide Chemical compound CC(=O)N(C)C(=O)N(C)C(C)=O BBJPLYGBSPMDOU-UHFFFAOYSA-N 0.000 description 1
- OFESGEKAXKKFQT-UHFFFAOYSA-N n-ethenyl-n-methylformamide Chemical compound C=CN(C)C=O OFESGEKAXKKFQT-UHFFFAOYSA-N 0.000 description 1
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
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- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
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- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VSVCAMGKPRPGQR-UHFFFAOYSA-N propan-2-one;sulfurous acid Chemical compound CC(C)=O.OS(O)=O VSVCAMGKPRPGQR-UHFFFAOYSA-N 0.000 description 1
- DQJSKCFIYCTPBV-UHFFFAOYSA-N propan-2-yl n-(propan-2-yloxycarbonylamino)peroxycarbamate Chemical compound CC(C)OC(=O)NOONC(=O)OC(C)C DQJSKCFIYCTPBV-UHFFFAOYSA-N 0.000 description 1
- 150000003212 purines Chemical class 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000004892 pyridazines Chemical class 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
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- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- URLJMZWTXZTZRR-UHFFFAOYSA-N sodium myristyl sulfate Chemical compound CCCCCCCCCCCCCCOS(O)(=O)=O URLJMZWTXZTZRR-UHFFFAOYSA-N 0.000 description 1
- 229950005425 sodium myristyl sulfate Drugs 0.000 description 1
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical class [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- KVSYNOOPFSVLNF-UHFFFAOYSA-M sodium;4-nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=C(S([O-])(=O)=O)C=C1 KVSYNOOPFSVLNF-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical compound C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
Definitions
- the present invention relates to novel copolymers having N-heterocyclic groups and their use in liquid and solid detergent formulations. These copolymers show in the washing process a color transfer inhibiting effect.
- copolymers described in these documents are characterized in part by a good inhibition of color transfer in washing processes. However, they generally have low compatibility with the other commonly used detergent ingredients. Thus, there is the danger of incompatibilities, for example in the form of turbidity or phase separations, especially in liquid detergents.
- the A) a polymeric graft base without monoethylenically unsaturated units and B) formed by polymerization of a cyclic, 3- to 7-membered N-vinylamide polymeric side chains contain, wherein the proportion of the side chains (B) in the total polymer ⁇ 60 wt .-% is.
- Similar graft polymers are disclosed in U.S. Pat DE 10156135 and the DE 10156133 described for this purpose.
- graft polymers are distinguished by improved compatibility with detergent constituents, in particular liquid detergents, the disadvantage of a poorer ink transfer inhibition is at the same time accepted for this advantage. In addition, the achieved compatibility is not completely satisfactory.
- the present invention relates to the use of such copolymers in liquid or solid detergent formulations comprising in polymerized form: (a) 80 to 99.9 mol% at least one monomer A, each comprising a heterocycle having at least 1 N atom (N-heterocycle) of 3 to 10 ring members and a C 2 -C 6 alkenyl group bonded to a C or N ring atom of the heterocycle; and (b) 0.1 to 20 mol% at least one monomer B which is copolymerizable with the monomer A and has a monoethylenically unsaturated double bond and a linear or branched poly-C 2 -C 4 -alkylene oxide group having on average 4 to 500 C 2 -C 4 -alkylene oxide units and 1 or 2, independently of one another comprises radicals selected from C 1 -C 2 -alkyl, wherein here and in the following all quantities of monomers in mol% are based on the total amount of monomers used to prepare the copo
- the invention also relates to such copolymers, with the proviso that the end group of the poly-C 2 -C 4 alkylene oxide group in the monomers B is selected from C 1 -C 2 -alkyl, when the monomer B is an ester of a ethylenically unsaturated carboxylic acid with a linear poly-C 2 -C 4 alkylene oxide.
- the invention further relates to a process for preparing such copolymers comprising the radical polymerization of at least one monomer A with the at least one monomer B.
- N-heterocycle is an aromatic or non-aromatic, heterocyclic radical having usually 3 to 10, in particular 4 to 8 and especially 5 to 7 ring atoms, where 1, 2 or 3 of the ring atoms are heteroatoms, preferably under nitrogen and oxygen are selected, wherein at least one ring member is a nitrogen atom.
- the N-heterocycle may be aromatic (heteroaryl) or partially or fully saturated.
- the N-heterocycle may optionally have one or more, for example, 1, 2, 3 or 4 substituents selected from C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl and phenyl.
- the N-heterocycle may have a carbonyl group and / or an N-oxide group as a ring member.
- the 3) N-heterocycle may also be present as a betainic structure in which at least one N atom of the heterocycle has a C 1 -C 20 -alkanediyl group with a lower -SO 3 - , -OSO 3 - , -COO - , -OPO (OH) O - , -OPO (OR f ) O - or -PO (OH) O - selected anionic group, wherein R f is C 1 -C 6 alkyl.
- C 1 -C 20 -alkanediyl here means a linear or branched aliphatic, two-membered, ie bonded via two carbon atoms, Hydrocarbon radical with usually 1 to 20 and in particular 1 to 10 C-atoms.
- alkyl for a linear or branched aliphatic hydrocarbon radical having usually 1 to 10, in particular 1 to 6 and especially 1 to 4 carbon atoms, such as.
- cycloalkyl for a cycloaliphatic hydrocarbon radical having usually 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
- alkenyl for a monoethylenically unsaturated hydrocarbon radical having generally 2 to 6 and in particular 2 to 3 carbon atoms, for.
- alkenyl is vinyl and allyl, particularly preferably allyl.
- C 2 -C 4 -alkylene oxide represents a linear or branched alkanedyloxy group having generally 2 to 4 and in particular 2 C atoms, such as CH 2 CH 2 O, (CH 2 ) 3 O, (CH 2 ) 4 O.
- the monomers A furthermore include N-vinylheterocyclic monomers having one of imidazoles, imidazolines and imidazolidines, pyridines, pyrroles, pyrrolidines, quinolines, isoquinolines, purines, pyrazoles, triazoles, tetrazoles, indolizines, pyridazines, pyrimidines, pyrazines, indoles, isoindoles, oxazoles , Oxazolidines, morpholines, piperazines, piperidines, isoxazoles, thiazoles, isothiazoles, indoxylene, isatins, dioxindoles and hydanthoines and derivatives thereof, eg barbituric acid, uracil and derivatives thereof, selected N-heterocycle.
- the monomers A different from the lactams III are also referred to below as monomers A2.
- the stated monomers A2 can also be used as betaine derivatives or quaternized products.
- N-heterocycles used in the monomers A2 are selected in particular from imidazoles, pyridines, pyridine-N-oxides and also betaine derivatives and quaternization products thereof, especially from imidazoles.
- Particularly preferred monomers A2 are N-vinylimidazole and C 1 -C 4 -alkylvinylimidazoles, for example N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole, in particular N-vinylimidazole and methylvinylimidazoles, especially N-vinylimidazole and N-vinyl-2-methylimidazole; 3-vinylimidazole-N-oxide; 2- and 4-vinylpyridines, eg 2-vinyl-4-methylpyridine, 2-vinyl-6-methylpyridine and 2- and 4-vinylpyridine; Vinylpyridine N-oxides, such as 2- and 4-vinylpyridine N-oxides, for example 2-vinyl-4-methylpyridine-N-oxide, 4-vinyl-2-methylpyridine-N-oxide and 2-
- Especially preferred betaine monomers A2 are monomers of the formula IV b, IV and IV e f, in which the group W 1 -X - is -CH 2 -COO -, - (CH 2) 2 -SO 3 - or - (CH 2 ) 3 -SO 3 - and R b , R c , R d , R e are each H.
- the quaternized monomers A2 used are preferably vinylimidazoles and vinylpyridines, these having been quaternized before or after the polymerization. Particular preference is given to using 1-methyl-3-vinylimidazolium methosulfate and methachloride.
- alkylating agents such as alkyl halides, which generally have 1 to 24 C atoms in the alkyl radical, or dialkyl sulfates, which generally contain alkyl radicals having 1 to 10 C atoms.
- alkylating agents such as alkyl halides, which generally have 1 to 24 C atoms in the alkyl radical, or dialkyl sulfates, which generally contain alkyl radicals having 1 to 10 C atoms.
- suitable alkylating agents from these groups are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and dimethyl sulfate and diethyl sulfate.
- alkylating agents are, for example, benzyl halides, in particular benzyl chloride and benzyl bromide; Chloroacetic acid; Fluorschwefelklaremethylester; diazomethane; Oxonium compounds such as trimethyloxonium tetrafluoroborate; Alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichlorohydrins.
- Preferred quaternizing agents are methyl chloride, dimethyl sulfate and diethyl sulfate.
- Suitable monomers A are furthermore mixtures of the abovementioned monomers A1 and A2.
- the monomers A are selected to be at least 85 mol% and especially 90 mol% among the monomers A1 (N-vinyllactams), and more preferably among N-vinylpyrrolidones.
- N-vinyllactam is N-vinylpyrrolidone.
- Particular preference is given to the N-vinyllactams and in particular N-vinylpyrrolidone as the sole monomer A.
- the monomers A comprise at least one N-vinyllactam as monomer A1 and at least one monomer A2 different therefrom, in particular an N-vinylimidazole.
- the molar ratio A1: A2 is then preferably in the range from 9: 1 to 1: 9, in particular 4: 1 to 1: 4.
- the monomers A are selected from N-vinylpyrrolidone and mixtures of N-vinylpyrrolidone with N-vinylimidazole.
- the proportion of the monomers A at least 85 mol% and in particular at least 90 mol% of the total amount of the monomers used for the preparation of the copolymers.
- the proportion of the monomers A based on the total amount of monomers, is from 85 mol% to 99.5 mol% and particularly preferably from 90 to 99 mol%.
- the proportion of ethylene oxide units in the poly-C 2 -C 4 -alkylene oxide group of the monomers B is chosen such that it contains at least 50 mol%, in particular 75 mol% and specifically about 100 mol% with respect to the C 2 -C 4 -alkylene oxide units contained in the monomer B.
- the poly-C 2 -C 4 alkylene oxide group of the monomers B naturally has 2 end groups in the case of a linear structure and 3 or more end groups in the case of a branched structure, one of which carries one ethylenically unsaturated group.
- the remaining terminal radicals (end groups) may be hydrogen or OH or an organic radical.
- Preferred organic end groups have 1 to 10 C atoms, in particular 1 to 4 C atoms, and are usually selected from H, C 1 -C 10 -alkyl and benzyl (or OH, C 1 -C 10 -alkyloxy and benzyloxy), in particular H and C 1 -C 4 -alkyl and especially C 1 -C 2 -alkyl.
- the monomers B preferably have 1 or 2 of such end groups and in particular 1 end group.
- the linear or branched poly-C 2 -C 4 -alkylene oxide groups Z generally have a degree of alkoxylation in the range from 4 to 500, in particular from 6 to 200 and especially from 6 to 100.
- alkanetriyl means a linear or branched aliphatic, trivalent, preferably bonded via three different carbon atoms hydrocarbon radical having generally 2 to 4, in particular 3 C-atoms.
- the radicals Z 2 or Z 2 and Z 3 are preferably each at least 50%, more preferably at least 75% and most preferably about 100% ethylene oxide units.
- radicals R 2 and R 3 in the formulas (II.1) and (II.2) are each independently of one another methyl.
- variable X is H and Y is C (O) O or C (O) NH.
- variable Z in formula (I) is in particular the structures of the formula (II.1) or (II.2) mentioned above as being preferred.
- R 1 is in particular H or methyl.
- Particular preference is given to the methylpoly-C 2 -C 3 -alkylene glycol esters of acrylic acid or of methacrylic acid and, among these, especially those having a proportion of at least 50 mol%, in particular at least 80 mol% of ethylene oxide groups, in each case based on the total amount of C 2 C 3 alkylene oxide groups, and especially methyl polyethylene glycol esters of (meth) acrylic acid.
- variable X is H and Y is CH 2 -O.
- variable Z in formula (I) is in particular the structures of the formula (II.1) or (II.2) mentioned above as being preferred.
- R 1 is in particular H or methyl.
- allyl ether C 2 -C 3 alkoxylates H
- the monomers B can be prepared by standard methods of organic chemistry known to the person skilled in the art (see, for example, US Pat. Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, 1954 ) are prepared, for. Example, by esterification, amidation, transamidation, transesterification or alkoxylation of suitable (meth) acrylic acids, (meth) acrylic esters, (meth) acrylamides and maleic acid, maleic acid (half) esters, maleic acid (half) amides; by alkoxylation of allyl alcohol; by etherification of allyl halides with poly-C 2 -C 4 -alkylene oxides and vinylation of polyalkylene oxides with OH or NH terminus with acetylene. Accordingly, in particular z.
- methyl polyethylene glycol (meth) acrylic acid can be obtained by esterification of (meth) acrylic acid with polyethylene glycol monomethyl ethers.
- Allyl alcohol polyalkoxylates suitable as monomers B are also commercially available, e.g. under the names Pluriol® A 010 R and Pluriol® A 11 RE from BASF Aktiengesellschaft.
- the proportion of the monomers B at most 15 mol.% And especially at most 10 mol .-% of the total amount of the monomers used to prepare the copolymers.
- the proportion of the monomers B is 0.5 to 15 mol .-% and particularly preferably 1 to 10 mol .-%.
- one or more further with the A and B monomers copolymerizable monomers C include: Examples of monomers C are monoethylenically unsaturated C 3 -C 10 monocarboxylic and C 4 -C 10 dicarboxylic acids, e.g.
- maleic anhydride For example, maleic anhydride; Amides of monoethylenically unsaturated C 3 -C 6 carboxylic acids with primary and secondary C 1 -C 12 amines, eg. B. (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide or N-butyl (meth) acrylamide; unsaturated nitriles, e.g. For example, acrylonitrile and methacrylonitrile; and the salts of said acids, the derivatives thereof and mixtures thereof.
- Amides of monoethylenically unsaturated C 3 -C 6 carboxylic acids with primary and secondary C 1 -C 12 amines eg. B.
- (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide or N-butyl (meth) acrylamide unsaturated nitriles, e
- the monomer C is selected from monoethylenically unsaturated C 3 -C 10 -mono- and C 4 -C 10 -dicarboxylic acids, in particular acrylic acid, methacrylic acid and maleic acid.
- the proportion of monomers C is less than 20 mol .-%, in particular less than 15 mol .-% and especially less than 10 mol .-%, based on the total weight of the copolymer.
- the proportion of the monomers C is 1 to 20 mol .-%, in particular 1 to 15 mol .-%, based on the total weight of the copolymer.
- the K values of the copolymers used according to the invention are usually from 10 to 150, preferably from 10 to 80 and more preferably from 15 to 60 (determined by H. Fikentscher, Cellulosic Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 ) in water or aqueous sodium chloride solutions at 25 ° C (concentration NaCl 0.1 to 7.0 wt .-%) and polymer concentrations, depending on the K value range at 0.1 wt .-% to 5 wt .-%. % lie).
- the respective desired K value can be adjusted by the composition of the starting materials.
- the present invention furthermore relates to a process for the preparation of the copolymers according to the invention in which the at least one monomer A is radically polymerized with the at least one monomer B and optionally with the monomers C.
- the free-radical polymerization of the monomers can be carried out by any known method, such as solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization, preferably the methods of solution polymerization and bulk polymerization, very particularly preferably solution polymerization.
- suitable organic solvents are aliphatic and cycloaliphatic monohydric C 1 -C 4 -alcohols, e.g. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol; polyhydric alcohols, such as C 1 -C 4 -glycols, for. Ethylene glycol, propylene glycol and butylene glycol and glycerin; Mono- and dialkyl ethers of polyhydric alcohols, such as C 1 -C 4 -alkyl ethers of said polyhydric alcohols, eg.
- Monomethylethyleneglycol monoethylethyleneglycol, dimethylethyleneglycol and dimethylpropyleneglycol
- Ether alcohols eg.
- cyclic ethers e.g. Eg dioxane
- Preferred organic solvents are alcohols.
- the polymerization is preferably carried out in an aqueous polymerization medium which contains at least 50% by volume, in particular at least 80% by volume and particularly preferably at least 95% by volume of water, based on the total amount of solvent. Particularly preferably, the polymerization is carried out in water.
- Suitable radical initiators are, in particular, peroxo compounds, azo compounds, redox initiator systems and reducing compounds. Of course you can also use mixtures of radical starters.
- thermally activatable polymerization initiators preference is given to initiators having a decomposition temperature ("10 h half-life decomposition temperature") in the range from 20 to 180 ° C., in particular from 50 to 120 ° C.
- thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and alkali metal sulfates, preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxy compounds, 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 permalate, tert-
- initiators can be used in combination with reducing compounds as starter / regulator systems.
- reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
- phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates
- sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
- Suitable examples are the combinations tert-butyl hydroperoxide / sodium disulfite and tert-butyl hydroperoxide / sodium hydroxymethanesulfinate; furthermore systems with addition small amounts of redox metal salts such as iron salts, eg ascorbic acid / iron (II) sulfate / sodium perox
- Preferred initiators are soluble in the amount used in the polymerization medium. Therefore, particularly water-soluble initiators are preferred. Particularly preferred initiators are the aforementioned diazo compounds, in particular water-soluble diazo compounds such as azobis (2-amidinopropane) dihydrochloride.
- photoinitiators e.g. Benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and their derivatives.
- the polymerization initiators are usually used in amounts of from 0.01 to 15% by weight, preferably from 0.25 to 5% by weight, based in each case on the monomers to be polymerized, and may be used singly or as Exploitation of beneficial synergistic effects in combination with each other.
- regulators conventional in the polymerization e.g. Mercapto compounds such as mercaptoethanol, thioglycolic acid, 1,4-bismercaptobutane-2,3-diol; Alkali metal sulfites and hydrogen sulfites such as sodium sulfite; Alkali metal phosphites and hypophosphites such as sodium hypophosphite, etc. are added.
- Suitable amounts of regulator are generally in the range of 0.01 to 5 wt .-%, based on the monomers to be polymerized.
- the polymerization temperature is generally in the range from 10 to 200.degree. C., preferably from 40 to 140.degree. C., more preferably from 50 to 120.degree.
- the polymerization may be carried out under atmospheric pressure, optionally it may also be carried out in a closed system under the evolving autogenous pressure.
- the production of the copolymers is followed by a chemical and / or physical deodorization, ie removal of unreacted monomers.
- physical deodorization the monomers are mixed with water vapor, e.g. B. by distilling off part of the aqueous polymerization medium and / or by passing superheated steam out of the polymerization mixture.
- chemical deodorization unreacted monomers in the reaction mixture are removed by use of more severe polymerization conditions, e.g. B. by the addition of further polymerization, often by addition of the above-mentioned redox initiators and especially by the addition of hydroperoxides, such as hydrogen peroxide and alkyl hydroperoxides, z.
- tert-butyl hydroperoxide in combination with reducing agents, in particular sulfur-containing reducing agents such as hydrogen sulfite, dithionite, adducts of bisulfite to ketones, such as the acetone-bisulfite adduct, hydroxymethanesulfinate and the like, optionally in the presence of traces of transition metals, eg Fe 2 + or Fe 3+ .
- sulfur-containing reducing agents such as hydrogen sulfite, dithionite
- adducts of bisulfite to ketones such as the acetone-bisulfite adduct, hydroxymethanesulfinate and the like
- transition metals eg Fe 2 + or Fe 3+
- polymer-analogous reaction z As polymer-analogous reaction z.
- transamidation, transesterification or alkoxylation in the polymer molecule contained (meth) acrylic acid units, (meth) acrylic acid ester units, (meth) acrylamide units and maleic acid units, maleic acid (half) ester units, maleic acid (half ) amide units, vinyl alcohol units, allyl alcohol units, vinylamine units and allylamine units, in particular the polymer-analogous esterification and amidation of (meth) acrylic acid units containing precursor polymers into consideration.
- copolymers of the invention based on (meth) acrylic acid esters or amides as components of the monomer units B, z.
- Example proceed by copolymerizing (meth) acrylic acid in an amount equivalent to the molar amount of the monomer B with the monomer A and optionally the monomer C and then the copolymer formed with polyalkylene glycols which are not end-capped, unilaterally by alkyl , Phenyl or alkylphenyl radicals end-capped or aminated on one side or end-capped on one side by alkyl, phenyl or alkylphenyl radicals and aminated on one side, esterified or aminated.
- a vinylpyridine N-oxide is used as monomer A, it has proven advantageous to first copolymerize the desired amount of the corresponding vinylpyridine compound with the other monomers and then to add the copolymerized vinylpyridine to vinylpyridine N-oxide units oxidize.
- copolymers according to the invention are outstandingly suitable as dye transfer inhibitors in the washing of colored textiles. They effectively reduce or prevent dye transfer between the textiles.
- copolymers according to the invention can be used universally in a wide variety of detergents, such as liquid and solid detergents or detergent formulations. In particular, they have a good compatibility with the usual detergent components, especially with regard to liquid detergents and detergent formulations.
- Good compatibility means, for the purposes of the present invention, that the copolymers according to the invention can easily be incorporated or formulated into detergent component formulations containing conventional components without segregation processes occurring, and that the resulting detergent formulations have good stability, in particular against segregation, within the usual life. In the case of liquid detergent formulations, this means, in particular, that no significant precipitation of the copolymers according to the invention takes place before or during use or turbidity does not occur.
- the copolymers of the invention are generally used in amounts ranging from 0.05 to 5 wt .-%, preferably 0.1 to 2 wt .-%, each based on the total weight of the detergent (formulations). They are suitable for both heavy-duty detergents and special detergents, such as color detergents. In color-preserving color detergents, they are usually used in amounts ranging from 0.1 to 1.5% by weight, preferably 0.1 to 1% by weight, based in each case on the total weight of the detergents (formulations).
- the detergents can be in solid form, for. B. in powder, granule, extrudate or tablet form, as a so-called compact detergent with a bulk density in the range of 500 to 950 g / l, or in liquid setting. They contain the anionic, nonionic and / or cationic surfactants commonly used in amounts of 2 to 50 wt .-%, preferably 8 to 30 wt .-%, each based on the total weight of the detergent (formulations). Particular preference is given to producing phosphate-free or reduced-phosphate detergents which have a phosphate content of at most 25% by weight, based in each case on the total weight of the detergent formulations (formulations), calculated as pentasodium tripolyphosphate.
- Suitable anionic surfactants are, for example, C 8 -C 22 , preferably C 10 -C 18, fatty alcohol sulfates, for example C 9 / C 11 -alcohol sulfate, C 12 / C 14 -alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.
- Suitable anionic surfactants are sulfated alkoxylated C 8 -C 22 -, preferably C 10 -C 18 -alcohols or their soluble salts.
- Compounds of this type are prepared, for example, by first alkoxylating the alcohol and then sulfating the alkoxylation product.
- Ethylene oxide is preferably used for the alkoxylation, with 2 to 50 mol, in particular 3 to 20 mol, of ethylene oxide being used per mole of fatty alcohol.
- the alkoxylation can also be carried out with propylene oxide or with butylene oxide.
- the alkylene oxides can also be used in combination.
- the alkoxylated alcohols may then contain the ethylene oxide, propylene oxide and / or butylene oxide units in the form of blocks or in random distribution.
- alkyl sulfonates in particular C 8 -C 24 - and especially C 10 -C 18 -alkyl sulfonates, and soaps, for example the salts of aliphatic C 8 -C 24 -carboxylic acids.
- anionic surfactants are linear C 9 -C 20 -alkylbenzenesulfonates (LAS).
- the anionic surfactants are preferably added to the detergent in the form of salts.
- Suitable cations are alkali metal ions, such as sodium, potassium and lithium ions, and ammonium ions, e.g. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium ions.
- nonionic surfactants are alkoxylated C 8 -C 22 -alcohols, in particular C 10 -C 18 -alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and guerbet alcohol alkoxylates.
- the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide.
- the alkoxylated alcohols may then contain the alkylene oxide units in the form of blocks or in random distribution. From 2 to 50, preferably from 3 to 20, moles of at least one of these alkylene oxides are used per mole of alcohol.
- the alkylene oxide used is preferably ethylene oxide.
- nonionic surfactants are alkylphenol alkoxylates, in particular C 6 -C 14 -alkylphenol ethoxylates containing on average 5 to 30 alkylene oxide units.
- nonionic surfactants are C 8 -C 22 -, in particular C 10 -C 18 -alkylpolyglucosides. These compounds contain 1 to 20, preferably 1.1 to 5 glucoside units.
- NT1 and NT2 in which D is C 6 -C 22 -alkyl, preferably C 10 -C 18 -alkyl
- E is hydrogen or C 1 -C 4 -alkyl, preferably methyl
- G is polyhydroxy-C 5 -C 12 -alkyl with at least 3 hydroxyl groups, preferably polyhydroxy-C 5 -C 6 alkyl.
- such compounds are obtained by acylation of reducing aminated sugars with acid chlorides of C 10 -C 18 carboxylic acids.
- the detergent formulations containing 3 to 12 moles of ethylene oxide ethoxylated C 10 -C 18 alcohols as nonionic surfactants.
- Particularly suitable cationic surfactants are, for example, C 7 -C 25 -alkylamines; C 7 -C 25 N, N-dimethyl-N- (hydroxyalkyl) ammonium salts; quaternized mono- and di- (C 7 -C 25 ) -alkyldimethylammonium compounds; Esterquats, such as quaternary esterified mono-, di- or trialkanolamines esterified with C 8 -C 22 carboxylic acids; and imidazoline quats such as 1-alkyl-imidazolinium salts of the general formulas KT1 or KT2: wherein R aa is C 1 -C 25 alkyl or C 2 -C 25 alkenyl, R bb is C 1 -C 4 alkyl or hydroxyalkyl and R cc is C 1 -C 4 alkyl, hydroxyalkyl or a radical R aa is - (CO) -W 2 - (
- the powdery and granular detergents and optionally also structured (multiphase) liquid detergents also contain one or more inorganic builders.
- Suitable inorganic builders are all commonly used compounds, such as aluminosilicates, silicates, carbonates and polyphosphates.
- crystalline and amorphous aluminosilicates with ion-exchanging properties such as zeolites, for example zeolite A, X, B, P, MAP and HS in their Na-form and in forms in which Na is partially exchanged for other cations, such as Li, K, Ca, Mg or ammonium.
- zeolites for example zeolite A, X, B, P, MAP and HS in their Na-form and in which Na is partially exchanged for other cations, such as Li, K, Ca, Mg or ammonium.
- silicates e.g. amorphous and crystalline silicates such as amorphous disilicates, sodium metasilicate, crystalline disilicates and layered silicates, e.g. the layered silicate SKS-6 (Clariant AG).
- the silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Preferably, Na, Li and Mg silicates are used.
- Carbonates and bicarbonates suitable as inorganic builders may also be used in the form of their alkali metal, alkaline earth metal and ammonium salts. Preference is given to sodium, lithium and magnesium carbonates and hydrogencarbonates, particular preference being given to sodium carbonate and / or sodium bicarbonate.
- the inorganic builders may be included in the detergents in amounts of from 5 to 60% by weight. They can be incorporated alone or in any combination with each other in the detergent. In powder and granular detergents, they are added in amounts of from 10 to 60% by weight, preferably from 20 to 50% by weight. In structured sossigwaschmittein inorganic builders in amounts up to 40 wt .-%, preferably up to 20 wt .-%, are used. They are suspended in the liquid formulation ingredients.
- the detergents contain one or more organic co-builders in addition to the inorganic builders.
- the organic co-builders are present in the powdered and granular as well as in the structured liquid detergent formulations in amounts of from 0.1 to 15% by weight, preferably from 0.25 to 8% by weight. In liquid detergent formulations, they are present in amounts of from 0.1 to 20% by weight and preferably from 0.25 to 10% by weight.
- the powdered and granular heavy-duty detergents may also contain a bleach system consisting of at least one bleach, optionally in combination with a bleach activator and / or a bleach catalyst.
- Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, as well as inorganic and organic peracids in the form of their alkali metal or magnesium salts or partly also in the form of the free acids.
- inorganic salts such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate
- inorganic and organic peracids in the form of their alkali metal or magnesium salts or partly also in the form of the free acids.
- suitable organic percarboxylic acids and their salts are Mg monoperphthalate, phthalimidopercaproic acid and dodecane-1,10-diacetic acid.
- An example of an inorganic peracid salt is K-peroxomonosulfate (oxone).
- bleaching agents are used, they are present in amounts of 5 to 30% by weight, preferably 10 to 25% by weight, in the formulations.
- Suitable bleach activators are, for example: acylamines, such as N, N, N ', N'-tetraacetylethylenediamine (TAED), tetraacetylglycoluril, N, N'-diacetyl-N, N'-dimethylurea and 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine; acylated lactams, such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam; substituted phenol esters of carboxylic acids such as Na-acetoxybenzenesulfonate, Na-octanoyloxybenzenesulfonate and sodium p-nonanoyloxybenzenesulfonate; N-Methylmorpholiniumacetonitrilmethylsulfat and hydrogen sulfate; acylated sugars
- bleach activators are used in detergents, they are present in amounts of from 0.1 to 15% by weight, preferably in amounts of from 1 to 8% by weight, more preferably in amounts of from 1.5 to 6% by weight ,
- Suitable bleach catalysts are quaternized imines and sulfonimines and Mn or Co complexes. If bleach catalysts are used in the detergent formulations, they are in amounts of up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active Mn complexes in amounts up to 0.1% by weight .-% contain.
- the detergents preferably contain an enzyme system. These are usually proteases, lipases, amylases or cellulases.
- the enzyme system may be limited to a single enzyme or may include a combination of different enzymes.
- the detergents are generally added amounts of 0.1 to 1.5 wt .-%, preferably 0.2 to 1 wt .-%, of the ready-made enzyme.
- Suitable proteases are e.g. Savinase and Esperase (manufactured by Novo Nordisk), a suitable lipase is e.g. Lipolase (manufactured by Novo Nordisk), a suitable cellulase is e.g. Celluzym (manufacturer also Novo Nordisk).
- the detergents also preferably contain soil release polymers and / or grayness inhibitors.
- soil release polymers are, for example, polyesters made from on one side with dihydric and / or polyhydric alcohols, in particular ethylene glycol and / or propylene glycol, closed polyethylene oxides (alcohol component) and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids (acid component).
- Further suitable soil-release polymers are amphiphilic graft copolymers and copolymers of vinyl and / or acrylic esters with or on polyalkylene oxides and modified celluloses, for example methylcellulose, hydroxypropylcellulose and carboxymethylcellulose.
- Preferably used soil release polymers are graft polymers of vinyl acetate on polyethylene oxide of average molecular weight M w 2500 to 8 000 in a weight ratio of 1.2: 1 to 3: 1, and commercially available polyethylene terephthalate / polyoxyethylene terephthalates of average molecular weight M w 3000 to 25000 from polyethylene oxides of average molecular weight M w 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate of 8: 1 to 1: 1 and block polycondensates containing blocks of (a) ester units of polyalkylene glycols of average molecular weight M w from 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units of aromatic dicarboxylic acids and polyhydric alcohols.
- These amphiphilic block polymers have average molecular weights M w of
- Grayness inhibitors and soil release polymers are in the detergent formulations in amounts of 0 to 2.5 wt .-%, preferably 0.2 to 1.5 wt .-%, particularly preferably 0.3 to 1.2 wt .-% , contain.
- copolymers according to the invention are suitable for the following applications: as brighteners in detergents, auxiliaries in textile production, adjuvants in cosmetic formulations, adjuvants in agrofuels, additives in water treatment, auxiliaries in metalworking agents and coolants and as gas hydrate inhibitors and in other fields of application oilfield.
- a reactor 800 g of distilled water were heated under nitrogen supply to about 82 ° C (T) internal temperature. Then, 360 g of vinylpyrrolidone (VP) and, in parallel, a mixture of 20.8 g of methacrylic acid (MAS), 19.2 g of ⁇ -methoxy-.omega.-methacryloylpolyethylene glycol (having a number-average molecular weight of polyethylene glycol (PEG) of about 1000) (MPEGMA). and 60 g of water (W1) within 3 h continuously (ie at a constant rate) added.
- VP vinylpyrrolidone
- MAS methacrylic acid
- MPEGMA ⁇ -methoxy-.omega.-methacryloylpolyethylene glycol
- W1 60 g of water (W1) within 3 h continuously (ie at a constant rate) added.
- Examples 2 to 10 were carried out analogously to Example 1, wherein in each case indicated in Table 1 below amounts of vinylpyrrolidone (VP), optionally as a mixture with the particular amount of vinylimidazole (VI), as well as methacrylic acid (MAS), ⁇ -Metoxy - ⁇ -methacryloylpolyethylene glycol (MPEGMA), water (W1 and W2) and 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) were used.
- VP vinylpyrrolidone
- VI vinylimidazole
- MAS methacrylic acid
- MPEGMA ⁇ -Metoxy - ⁇ -methacryloylpolyethylene glycol
- Example 19 was carried out analogously to Example 18.
- Example 21 was carried out analogously to Example 20.
- Example 22 was carried out analogously to Example 23, but no mercaptoethanol (ME) was added.
- the copolymers of the invention were tested as color transfer inhibitors in detergents.
- WM 1 0 , 15 wt%
- WM2 0.25 wt%
- WM3 0.15 wt%
- WM4 1 wt%).
- white cotton test fabric under the washing conditions mentioned in Table 4 in the presence of dye which was added to the wash liquor as 0.03 or 0.06 wt.% Aqueous solution, washed.
- the staining of the test fabric was measured photometrically using the Elrepho 2000 photometer (Datacolor).
- the remission (in%) was measured at the wavelength of the respective maximum absorption of the different dyes.
- the whiteness of the test fabric after the wash was used to evaluate staining.
- the measured values given in Table 5 a - c were confirmed by multiple repetition and averaging.
- Table 5 a - c shows the results of the wash tests with copolymers according to the invention in comparison with washing tests without dye transfer inhibitor.
- Table 3 ⁇ / b> Compositions of detergents WM1 to WM4 (in% by weight) WM 1 [%] WM 2 [%] WM 3 [%] WM 4 [%] C 12 / C 14 fatty alcohol sulfate 24 24 C 12 / C 14 fatty alcohol ethoxylate 2 2 C 12 / C 14 alkyl benzene sulfonate 9 9 C 13 / C 15 - tallow fatty alcohol reacted with 7 EO units 6.6 6.6 6 6 coconut fatty acid 5 5 Soap 1.8 1.8 0.7 0.7 borax 2.2 2.2 Zeolite A 45 45 Polycarboxylate (acrylic acid / maleic acid copolymer; w / w 70:30, M w 70000) 5 5 sodium 7 7 7 Trisodium citrate x 2 H 2 O 12 12 12
- Table 6 summarizes the visual ratings after 4 weeks storage at 40 ° C. ⁇ b> Table 6: ⁇ / b> Copolymer Example No. WM 4 without clear Copolymer 1 clear Copolymer 3 clear Copolymer 9 clear Copolymer 10 clear Copolymer 11 clear Copolymer 22 clear Copolymer 23 clear
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Abstract
Description
Die vorliegende Erfindung betrifft neue Copolymere mit N-heterocyclischen Gruppen und ihre Verwendung in flüssigen und festen Waschmittelformulierungen. Diese Copolymere zeigen im Waschprozess eine die Farbübertragung inhibierende Wirkung.The present invention relates to novel copolymers having N-heterocyclic groups and their use in liquid and solid detergent formulations. These copolymers show in the washing process a color transfer inhibiting effect.
Während des Waschvorgangs werden von gefärbten Textilien oft Farbstoffmoleküle abgelöst, die wiederum auf andere Textilien aufziehen können. Um dieser unerwünschten Farbübertragung entgegenzuwirken, werden oftmals sogenannte Farbübertragungsinhibitoren eingesetzt. Hierbei handelt es sich häufig um Polymere, die Monomere mit stickstoffheterocyclischen Resten (= N-heterocyclische Gruppen bzw. N-Heterocyclen) einpolymerisiert enthalten.During the washing process dyed textiles often replace dye molecules, which in turn can be applied to other textiles. To counteract this undesirable color transfer, so-called color transfer inhibitors are often used. These are often polymers which contain monomers with nitrogen-heterocyclic radicals (= N-heterocyclic groups or N-heterocycles) in copolymerized form.
So beschreibt z. B. die
Ähnliche Copolymere werden zu diesem Zweck in der
Die in diesen Schriften beschriebenen Copolymere zeichnen sich zum Teil durch eine gute Inhibierung der Farbübertragung in Waschprozessen aus. Sie besitzen im Allgemeinen jedoch eine geringe Verträglichkeit mit den weiteren üblicherweise verwendeten Waschmittelbestandteilen. So besteht insbesondere bei Flüssigwaschmitteln die Gefahr von Unverträglichkeiten, zum Beispiel in Form von Trübungen oder Phasenseparationen.The copolymers described in these documents are characterized in part by a good inhibition of color transfer in washing processes. However, they generally have low compatibility with the other commonly used detergent ingredients. Thus, there is the danger of incompatibilities, for example in the form of turbidity or phase separations, especially in liquid detergents.
Zur Lösung der Verträglichkeitsproblematik werden in der
Zwar zeichnen sich derartige Pfropfpolymere durch eine verbesserte Verträglichkeit mit Waschmittelbestandteilen, insbesondere von Flüssigwaschmitteln, aus, jedoch wird für diesen Vorteil gleichzeitig der Nachteil einer schlechteren Farbübertragungsinhibierung in Kauf genommen. Zudem ist die erzielte Verträglichkeit nicht vollständig zufriedenstellend.Although such graft polymers are distinguished by improved compatibility with detergent constituents, in particular liquid detergents, the disadvantage of a poorer ink transfer inhibition is at the same time accepted for this advantage. In addition, the achieved compatibility is not completely satisfactory.
Aus der älteren deutschen Patentanmeldung
Es war daher Aufgabe der vorliegenden Erfindung, Polymere mit einer guten eine Farbübertragung beim Waschvorgang inhibierenden Wirkung bereitzustellen, die eine gute Verträglichkeit mit herkömmlichen Waschmittelbestandteilen, insbesondere bei flüssigen Waschmittelformulierungen, besitzen.It was therefore an object of the present invention to provide polymers having a good ink transfer during the washing process inhibiting effect, which have a good compatibility with conventional detergent ingredients, especially in liquid detergent formulations.
Es wurde überraschend gefunden, dass diese Aufgabe durch Copolymere auf Basis von Monomeren mit N-Heterocyclen (Monomere A) gelöst wird, die ethylenisch ungesättigte Monomere B mit Polyalkylenoxid-Gruppen in einer Menge von 0,1 bis 20 mol-% einpolymerisiert enthalten.It has surprisingly been found that this object is achieved by copolymers based on monomers with N-heterocycles (monomers A) which contain copolymerized ethylenically unsaturated monomers B with polyalkylene oxide groups in an amount of 0.1 to 20 mol%.
Dementsprechend betrifft die vorliegende Erfindung die Verwendung derartiger Copolymeren in flüssigen oder festen Waschmittelformulierungen, umfassend in polymerisierter Form:
Die Erfindung betrifft außerdem derartige Copolymere, mit der Maßgabe, dass die Endgruppe der Poly-C2-C4-alkylenoxidgruppe in den Monomeren B unter C1-C2-Alkyl ausgewählt ist, wenn es sich bei dem Monomer B um einen Ester einer ethylenisch ungesättigten Carbonsäure mit einem linearen Poly-C2-C4-Alkylenoxid handelt. Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung derartiger Copolymere umfassend die radikalische Polymerisation mindestens eines Monomers A mit dem mindestens einen Monomer B.The invention also relates to such copolymers, with the proviso that the end group of the poly-C 2 -C 4 alkylene oxide group in the monomers B is selected from C 1 -C 2 -alkyl, when the monomer B is an ester of a ethylenically unsaturated carboxylic acid with a linear poly-C 2 -C 4 alkylene oxide. The invention further relates to a process for preparing such copolymers comprising the radical polymerization of at least one monomer A with the at least one monomer B.
Hier und im Folgenden steht N-Heterocyclus für einen aromatischen oder nichtaromatischen, heterocyclischen Rest mit in der Regel 3 bis 10, insbesondere 4 bis 8 und speziell 5 bis 7 Ringatomen, wobei 1, 2 oder 3 der Ringatome Heteroatome sind, die vorzugsweise unter Stickstoff und Sauerstoff ausgewählt sind, wobei mindestens 1 Ringglied ein Stickstoffatom ist. Der N-Heterocyclus kann aromatisch (Heteroaryl) oder teilweise oder vollständig gesättigt sein. Des Weiteren kann der N-Heterocyclus gegebenenfalls einen oder mehrere, z.B. 1, 2, 3 oder 4 unter C1-C4-Alkyl, C3-C6-Cycloalkyl und Phenyl ausgewählte Substituenten aufweisen. Weiterhin kann der N-Heterocyclus eine Carbonylgruppe und/oder eine N-Oxid-Gruppe als Ringglied aufweisen. Im Übrigen kann der N-Heterocyclus in quaternisierter Form, z. B. durch Alkylierung wenigstens eines N-Ringatoms, vorliegen. Darüber hinaus kann der 3) N-Heterocylus auch als betainische Struktur vorliegen, bei der wenigstens ein N-Atom des Heterocyclus über eine C1-C20-Alkandiylgruppe mit einer unter -SO3 -, -OSO3 -, -COO-, -OPO(OH)O-, -OPO(ORf)O- oder -PO(OH)O- ausgewählten anionischen Gruppe verbrückt ist, wobei Rf für C1-C6-Alkyl steht. C1-C20-Alkandiyl bedeutet hier einen linearen oder verzweigten aliphatischen, zweibindingen, d. h. über zwei C-Atome gebundenen, Kohlenwasserstoffrest mit in der Regel 1 bis 20 und insbesondere 1 bis 10 C-atomen.Here and below, N-heterocycle is an aromatic or non-aromatic, heterocyclic radical having usually 3 to 10, in particular 4 to 8 and especially 5 to 7 ring atoms, where 1, 2 or 3 of the ring atoms are heteroatoms, preferably under nitrogen and oxygen are selected, wherein at least one ring member is a nitrogen atom. The N-heterocycle may be aromatic (heteroaryl) or partially or fully saturated. Furthermore, the N-heterocycle may optionally have one or more, for example, 1, 2, 3 or 4 substituents selected from C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl and phenyl. Furthermore, the N-heterocycle may have a carbonyl group and / or an N-oxide group as a ring member. Incidentally, the N-heterocycle in quaternized form, for. B. by alkylation of at least one N-ring atom, are present. In addition, the 3) N-heterocycle may also be present as a betainic structure in which at least one N atom of the heterocycle has a C 1 -C 20 -alkanediyl group with a lower -SO 3 - , -OSO 3 - , -COO - , -OPO (OH) O - , -OPO (OR f ) O - or -PO (OH) O - selected anionic group, wherein R f is C 1 -C 6 alkyl. C 1 -C 20 -alkanediyl here means a linear or branched aliphatic, two-membered, ie bonded via two carbon atoms, Hydrocarbon radical with usually 1 to 20 and in particular 1 to 10 C-atoms.
Hier und im Folgenden steht Alkyl für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit in der Regel 1 bis 10, insbesondere 1 bis 6 und speziell 1 bis 4 C-Atomen, wie z. B. Methyl, Ethyl, n-Propyl, 1-Methylethyl, n-Butyl, 1-Methylpropyl, 2-Methylpropyl, 1,1-Dimethylethyl, n-Pentyl, 1-Methylbutyl, 2-ethylbutyl, 3-Methylbutyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 1,1-Dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyi, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl, 1-Ethyl-3-methylpropyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, 1-Methylhexyl, 1-Ethylhexyl, 2-Ethylhexyl, 1-Methylheptyl, 1-Methyloctyl oder 1-Methylnonyl:Here and below is alkyl for a linear or branched aliphatic hydrocarbon radical having usually 1 to 10, in particular 1 to 6 and especially 1 to 4 carbon atoms, such as. Methyl, ethyl, n -propyl, 1-methylethyl, n -butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n -pentyl, 1-methylbutyl, 2-ethylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2- Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-3-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 1-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 1-methylheptyl, 1-methyloctyl or 1-methylnonyl:
Hier und im Folgenden steht Cycloalkyl für einen cycloaliphatischen Kohlenwasserstoffrest mit in der Regel 3 bis 6 C-Atomen, wie z B. Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl.Here and below is cycloalkyl for a cycloaliphatic hydrocarbon radical having usually 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Hier und im Folgenden steht Alkenyl für einen monoethylenisch ungesättigten Kohlenwasserstoffrest mit in der Regel 2 bis 6 und insbesondere 2 bis 3 C-Atomen, z. B. für Vinyl, Propen-1-yl, Propen-2-yl, Allyl, 1-Buten-1-yl, 1-Buten-2-yl, 2-Methylpropen-3-yl (Methallyl), 1-Penten-2-yl und 1-Hexen-2-yl. Insbesondere steht Alkenyl für Vinyl und Allyl, besonders bevorzugt für Allyl.Here and below is alkenyl for a monoethylenically unsaturated hydrocarbon radical having generally 2 to 6 and in particular 2 to 3 carbon atoms, for. Vinyl, propen-1-yl, propen-2-yl, allyl, 1-buten-1-yl, 1-buten-2-yl, 2-methyl-propen-3-yl (methallyl), 1-pentene 2-yl and 1-hexen-2-yl. In particular, alkenyl is vinyl and allyl, particularly preferably allyl.
C2-C4-Alkylenoxid steht für eine lineare oder verzweigte Alkandiyloxy-Gruppe mit in der Regel 2 bis 4 und insbesondere 2 C-Atomen, wie CH2CH2O, (CH2)3O, (CH2)4O, CH(CH3)-CH2O, CH2-CH(CH3)O, CH2-C(CH3)2O, CH(CH3)-CH(CH3)-O, C(CH3)2-CH2O, CH2CH(CH3)-CH2O, CH(CH3)-(CH2)2O und (CH2)2-CH(CH3)O, insbesondere für eine der vorgenannten Alkan-1,2-diyloxy-Gruppen und speziell für CH2CH2O.C 2 -C 4 -alkylene oxide represents a linear or branched alkanedyloxy group having generally 2 to 4 and in particular 2 C atoms, such as CH 2 CH 2 O, (CH 2 ) 3 O, (CH 2 ) 4 O. , CH (CH 3 ) -CH 2 O, CH 2 -CH (CH 3 ) O, CH 2 -C (CH 3 ) 2 O, CH (CH 3 ) -CH (CH 3 ) -O, C (CH 3 ) 2 -CH 2 O, CH 2 CH (CH 3 ) -CH 2 O, CH (CH 3 ) - (CH 2 ) 2 O and (CH 2 ) 2 -CH (CH 3 ) O, in particular for one of the abovementioned Alkane-1,2-diyloxy groups and especially for CH 2 CH 2 O.
Zu den Monomeren A zählen cyclische Lactame, die an ihrem Stickstoffatom einen C2-C6-Alkenylrest, insbesondere einen Vinylrest tragen. Derartige Lactame können durch die allgemeine Formel (III)
- x
- für eine ganze Zahl im Bereich von 1 bis 6 steht; und
- Ra
- für H oder C1-C4-Alkyl steht;
- x
- is an integer in the range of 1 to 6; and
- R a
- is H or C 1 -C 4 alkyl;
Zu den Monomeren A zählen weiterhin N-Vinylheterocyclische Monomere mit einem unter Imidazolen, Imidazolinen und Imidazolidinen, Pyridinen, Pyrrolen, Pyrrolidinen, Chinolinen, lsochinolinen, Purinen, Pyrazolen, Triazolen, Tetraazolen, Indolizinen, Pyridazinen, Pyrimidinen, Pyrazinen, Indolen, Isoindolen, Oxazolen, Oxazolidinen, Morpholinen, Piperazinen, Piperidinen, Isoxazolen, Thiazolen, Isothiazolen, Indoxylen, Isatinen, Dioxindolen und Hydanthoinen sowie deren Derivaten, z.B. Barbitursäure, Uracil und deren Derivaten, ausgewählten N-Heterocyclus. Die von den Lactamen III verschiedenen Monomere A werden im Folgenden auch als Monomere A2 bezeichnet.The monomers A furthermore include N-vinylheterocyclic monomers having one of imidazoles, imidazolines and imidazolidines, pyridines, pyrroles, pyrrolidines, quinolines, isoquinolines, purines, pyrazoles, triazoles, tetrazoles, indolizines, pyridazines, pyrimidines, pyrazines, indoles, isoindoles, oxazoles , Oxazolidines, morpholines, piperazines, piperidines, isoxazoles, thiazoles, isothiazoles, indoxylene, isatins, dioxindoles and hydanthoines and derivatives thereof, eg barbituric acid, uracil and derivatives thereof, selected N-heterocycle. The monomers A different from the lactams III are also referred to below as monomers A2.
Die genannten Monomere A2 können auch als betainische Derivate oder quaternisierte Produkte eingesetzt werden.The stated monomers A2 can also be used as betaine derivatives or quaternized products.
In den Monomeren A2 verwendete N-Heterocyclen sind insbesondere unter Imidazolen, Pyridinen, Pyridin-N-oxiden sowie betainischen Derivaten und Quaternisierungsprodukten davon, speziell unter Imidazolen ausgewählt.N-heterocycles used in the monomers A2 are selected in particular from imidazoles, pyridines, pyridine-N-oxides and also betaine derivatives and quaternization products thereof, especially from imidazoles.
In einer bevorzugten Ausführungsform sind die Monomere A2 unter N-Vinylimidazolen der allgemeinen Formel IV a, betainischen N-Vinylimidazolen der allgemeinen Formel IV b, 2- und 4-Vinylpyridinen der allgemeinen Formeln IV c und IV d sowie betainischen 2- und 4-Vinylpyridinen der allgemeinen Formeln IV e und IV f ausgewählt:
- Rb, Rc, Rd, Re
- jeweils unabhängig voneinander für H, C1-C4-Alkyl oder Phenyl, bevorzugt H oder C1-C4-Alkyl, besonders bevorzugt H stehen;
- W1
- für C1-C20-Alkylen, beispielsweise -CH2-, -CH(CH3)-, -(CH2)2-, -CH2- CH(CH3)-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH3)6-, vorzugsweise C1-C3- Alkylen; insbesondere -CH2-, -(CH2)2- oder -(CH2)3- steht;
- Q-
- für -SO3 -, -OSO3 - , -COO-, -OPO(OH)O-, -OPO(ORf)O- oder -PO(OH)O- steht; und
- Rf
- für C1-C24-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso- Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo- Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n- Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C1-C4-Alkyl steht.
- R b, R c, R d, R e
- each independently of one another are H, C 1 -C 4 -alkyl or phenyl, preferably H or C 1 -C 4 -alkyl, particularly preferably H;
- W 1
- for C 1 -C 20 -alkylene, for example -CH 2 -, -CH (CH 3 ) -, - (CH 2 ) 2 -, -CH 2 -CH (CH 3 ) -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 3 ) 6 -, preferably C 1 -C 3 - alkylene; in particular -CH 2 -, - (CH 2 ) 2 - or - (CH 2 ) 3 -;
- Q -
- is -SO 3 - , -OSO 3 - , -COO - , -OPO (OH) O - , -OPO (OR f ) O - or -PO (OH) O - ; and
- R f
- for C 1 -C 24 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; C 1 -C 4 -alkyl is particularly preferred.
Besonders bevorzugte Monomere A2 sind N-Vinylimidazol und C1-C4-Alkylvinylimidazole, z.B. N-Vinyl-2-methylimidazol, N-Vinyl-4-methylimidazol, N-Vinyl-5-methylimidazol, N-Vinyl-2-ethylimidazol, insbesondere N-Vinylimidazol und Methylvinylimidazole, speziell N-Vinylimidazol und N-Vinyl-2-methylimidazol; 3-Vinylimidazol-N-oxid; 2- und 4-Vinylpyridine, z.B. 2-Vinyl-4-methylpyridin, 2-Vinyl-6-methylpyridin und 2-und 4-Vinylpyridin; Vinylpyridin-N-oxide, wie 2- und 4-Vinylpyridin-N-oxide, z.B. 2-Vinyl-4-methylpyridin-N-oxid, 4-Vinyl-2-methylpyridin-N-oxid und 2- und 4-Vinylpyridin-N-oxid; sowie betainische Derivate und Quatemisierungsprodukte davon.Particularly preferred monomers A2 are N-vinylimidazole and C 1 -C 4 -alkylvinylimidazoles, for example N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole, in particular N-vinylimidazole and methylvinylimidazoles, especially N-vinylimidazole and N-vinyl-2-methylimidazole; 3-vinylimidazole-N-oxide; 2- and 4-vinylpyridines, eg 2-vinyl-4-methylpyridine, 2-vinyl-6-methylpyridine and 2- and 4-vinylpyridine; Vinylpyridine N-oxides, such as 2- and 4-vinylpyridine N-oxides, for example 2-vinyl-4-methylpyridine-N-oxide, 4-vinyl-2-methylpyridine-N-oxide and 2- and 4-vinylpyridine N-oxide; and betaine derivatives and quaternization products thereof.
Besonders bevorzugte betainische Monomere A2 sind Monomere der Formeln IV b, IV e und IV f, in denen die Gruppierung W1-X- für -CH2-COO-, -(CH2)2-SO3 - oder -(CH2)3-SO3 - steht und Rb, RC, Rd, Re jeweils für H stehen.Especially preferred betaine monomers A2 are monomers of the formula IV b, IV and IV e f, in which the group W 1 -X - is -CH 2 -COO -, - (CH 2) 2 -SO 3 - or - (CH 2 ) 3 -SO 3 - and R b , R c , R d , R e are each H.
Als quaternisierte Monomere A2 werden bevorzugt Vinylimidazole und Vinylpyridine verwendet, wobei diese vor oder nach der Polymerisation quaternisiert wurden. Besonders bevorzugt werden 1-Methyl-3-vinylimidazoliummethosulfat und -methochlorid verwendet.The quaternized monomers A2 used are preferably vinylimidazoles and vinylpyridines, these having been quaternized before or after the polymerization. Particular preference is given to using 1-methyl-3-vinylimidazolium methosulfate and methachloride.
Die Quaternisierung kann insbesondere mit Alkylierungsmitteln wie Alkylhalogeniden, die in der Regel 1 bis 24 C-Atome im Alkylrest aufweisen, oder Dialkylsulfaten, die im allgemeinen Alkylreste mit 1 bis 10 C-Atomen enthalten, vorgenommen werden. Beispiele für geeignete Alkylierungsmittel aus diesen Gruppen sind Methylchlorid, Methylbromid, Methyliodid, Ethylchlorid, Ethylbromid, Propylchlorid, Hexylchlorid, Dodecylchlorid, Laurylchlorid sowie Dimethylsulfat und Diethylsulfat. Weitere geeignete Alkylierungsmittel sind z.B. Benzylhalogenide, insbesondere Benzylchlorid und Benzylbromid; Chloressigsäure; Fluorschwefelsäuremethylester; Diazomethan; Oxoniumverbindungen, wie Trimethyloxoniumtetrafluoroborat; Alkylenoxide, wie Ethylenoxid, Propylenoxid und Glycidol, die in Gegenwart von Säuren zum Einsatz kommen; kationische Epichlorhydrine. Bevorzugte Quaternisierungsmittel sind Methylchlorid, Dimethylsulfat und Diethylsulfat.The quaternization can be carried out in particular with alkylating agents such as alkyl halides, which generally have 1 to 24 C atoms in the alkyl radical, or dialkyl sulfates, which generally contain alkyl radicals having 1 to 10 C atoms. Examples for suitable alkylating agents from these groups are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and dimethyl sulfate and diethyl sulfate. Further suitable alkylating agents are, for example, benzyl halides, in particular benzyl chloride and benzyl bromide; Chloroacetic acid; Fluorschwefelsäuremethylester; diazomethane; Oxonium compounds such as trimethyloxonium tetrafluoroborate; Alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichlorohydrins. Preferred quaternizing agents are methyl chloride, dimethyl sulfate and diethyl sulfate.
Als Monomere A kommen weiterhin Mischungen der vorgenannten Monomere A1 und A2 in Betracht.Suitable monomers A are furthermore mixtures of the abovementioned monomers A1 and A2.
In einer bevorzugten Ausführungsform sind die Monomere A zu wenigstens 85 mol.-% und speziell 90 mol.-% unter den Monomeren A1 (N-Vinyllactamen) und besonders bevorzugt unter N-Vinylpyrrolidonen ausgewählt. Ganz besonders bevorzugtes N-Vinyllactam ist N-Vinylpyrrolidon. Besonders bevorzugt sind die N-Vinyllactame und insbesondere N-Vinylpyrrolidon als alleiniges Monomer A.In a preferred embodiment, the monomers A are selected to be at least 85 mol% and especially 90 mol% among the monomers A1 (N-vinyllactams), and more preferably among N-vinylpyrrolidones. Very particularly preferred N-vinyllactam is N-vinylpyrrolidone. Particular preference is given to the N-vinyllactams and in particular N-vinylpyrrolidone as the sole monomer A.
In einer weiteren bevorzugten Ausführungsform umfassen die Monomere A wenigstens ein N-Vinyllactam als Monomer A1 und wenigstens ein davon verschiedenes Monomer A2, insbesondere ein N-Vinylimidazol. Das Molverhältnis A1:A2 liegt dann vorzugsweise im Bereich von 9:1 bis 1:9, insbesondere 4:1 bis 1:4.In a further preferred embodiment, the monomers A comprise at least one N-vinyllactam as monomer A1 and at least one monomer A2 different therefrom, in particular an N-vinylimidazole. The molar ratio A1: A2 is then preferably in the range from 9: 1 to 1: 9, in particular 4: 1 to 1: 4.
In einer besonders bevorzugten Ausführungsform sind die Monomere A unter N-Vinylpyrrolidon und Gemischen aus N-Vinylpyrrolidon mit N-Vinylimidazol ausgewählt.In a particularly preferred embodiment, the monomers A are selected from N-vinylpyrrolidone and mixtures of N-vinylpyrrolidone with N-vinylimidazole.
Für die farbübertragungsinhibierende Wirkung der erfindungsgemäßen Copolymere hat es sich als vorteilhaft erwiesen, wenn der Anteil der Monomere A wenigstens 85 mol-% und insbesondere wenigstens 90 mol-% der Gesamtmenge der zur Herstellung der Copolymere eingesetzten Monomere ausmacht. Insbesondere beträgt der Anteil der Monomere A, bezogen auf die Gesamtmonomermenge, 85 mol-% bis 99,5 mol-% und besonders bevorzugt 90 bis 99 mol-%.For the dye transfer-inhibiting effect of the copolymers of the invention, it has proved to be advantageous if the proportion of the monomers A at least 85 mol% and in particular at least 90 mol% of the total amount of the monomers used for the preparation of the copolymers. In particular, the proportion of the monomers A, based on the total amount of monomers, is from 85 mol% to 99.5 mol% and particularly preferably from 90 to 99 mol%.
Es hat sich weiterhin für die erfindungsgemäßen Zwecke als vorteilhaft erwiesen, wenn der Anteil an Ethylenoxid-Einheiten in der Poly-C2-C4-alkylenoxidgruppe der Monomere B so gewählt wird, dass er mindestens 50 mol-%, insbesondere 75 mol-% und speziell etwa 100 mol-% bezüglich der im Monomer B enthaltenen C2-C4-Alkylenoxid-Einheiten beträgt.It has furthermore proved to be advantageous for the purposes according to the invention if the proportion of ethylene oxide units in the poly-C 2 -C 4 -alkylene oxide group of the monomers B is chosen such that it contains at least 50 mol%, in particular 75 mol% and specifically about 100 mol% with respect to the C 2 -C 4 -alkylene oxide units contained in the monomer B.
Die Poly-C2-C4-alkylenoxidgruppe der Monomere B weist naturgemäß im Falle einer linearen Strukur 2 Endgruppen und im Falle einer verzweigten Struktur 3 oder mehr Endgruppen auf, wovon eine eine ethylenisch ungesättigte Gruppe trägt. Die verbleibenden endständigen Reste (Endgruppen) können Wasserstoff bzw. OH oder ein organischer Rest sein. Bevorzugte organische Endgruppen weisen 1 bis 10 C-Atome insbesondere 1 bis 4 C-Atome auf und sind üblicherweise ausgewählt unter H, C1-C10-Alkyl und Benzyl (bzw. OH, C1-C10-Alkyloxy und Benzyloxy), insbesondere unter H und C1-C4-Alkyl und speziell unter C1-C2-Alkyl. Vorzugsweise weisen die Monomere B 1 oder 2 derartiger Endgruppen und insbesondere 1 Endgruppe auf.The poly-C 2 -C 4 alkylene oxide group of the monomers B naturally has 2 end groups in the case of a linear structure and 3 or more end groups in the case of a branched structure, one of which carries one ethylenically unsaturated group. The remaining terminal radicals (end groups) may be hydrogen or OH or an organic radical. Preferred organic end groups have 1 to 10 C atoms, in particular 1 to 4 C atoms, and are usually selected from H, C 1 -C 10 -alkyl and benzyl (or OH, C 1 -C 10 -alkyloxy and benzyloxy), in particular H and C 1 -C 4 -alkyl and especially C 1 -C 2 -alkyl. The monomers B preferably have 1 or 2 of such end groups and in particular 1 end group.
Efindungsgemäß geeignete Monomere B weisen bevorzugt die allgemeine Formel (1) auf:
X-CH=CR1-Y-Z (I),
worin
- X
- für H oder COOH steht;
- R1
- für C1-C4-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec- Butyl und tert-Butyl, insbesondere H oder Methyl steht;
- Y
- für O, CH2-O, C(O)O, C(O)NH, NHC(O) oder CH2-NHC(O) steht; und
- Z
- für eine lineare oder verzweigte Poly-C2-C4-Alkylenoxidgruppe steht, umfassend im Mittel 4 bis 500 C2-C4-Alkylenoxideinheiten und 1 oder 2 endständige, unab- hängig voneinander unter H, C1-C10-Alkyl und Benzyl, vorzugsweise unter H und C1-C4-Alkyl und speziell unter C1-C2-Alkyl ausgewählte Reste.
X-CH = CR 1 -YZ (I),
wherein
- X
- is H or COOH;
- R 1
- C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, in particular H or methyl;
- Y
- O, CH 2 -O, C (O) O, C (O) NH, NHC (O) or CH 2 -NHC (O); and
- Z
- represents a linear or branched poly-C 2 -C 4 -alkylene oxide group comprising on average 4 to 500 C 2 -C 4 -alkylene oxide units and 1 or 2 terminal, independently of one another by H, C 1 -C 10 -alkyl and Benzyl, preferably selected from H and C 1 -C 4 alkyl and especially C 1 -C 2 alkyl radicals.
Sofern die Orientierung der Reste Y beim Einbau in die Formel (I) auf unterschiedliche Weise realisiert werden kann, so erfolgt der Einbau in der oben angegebenen Weise von links nach rechts gelesen.If the orientation of the radicals Y during incorporation into the formula (I) can be realized in different ways, then the installation is carried out in the manner indicated above from left to right.
Bei der Angabe der Anzahl an C2-C4-Alkylenoxid-Einheiten in der linearen oder verzweigten Poly-C2-C4-Alkylenoxidgruppe Z bezieht sich der Ausdruck "im Mittel" hier und im Folgenden auf das Zahlenmittel der Alkylenoxideinheiten pro Monomer B. Synonym wird auch der Begriff Alkoxylierungsgrad verwendet.When referring to the number of C 2 -C 4 -alkylene oxide units in the linear or branched poly-C 2 -C 4 -alkylene oxide group Z, the term "on average" here and below refers to the number average of the alkylene oxide units per monomer B The term "degree of alkoxylation" is also used synonymously.
Die linearen oder verzweigten Poly-C2-C4-Alkylenoxidgruppen Z weisen in der Regel einen Alkoxylierungsgrad im Bereich von 4 bis 500, insbesondere von 6 bis 200 und speziell von 6 bis 100 auf.The linear or branched poly-C 2 -C 4 -alkylene oxide groups Z generally have a degree of alkoxylation in the range from 4 to 500, in particular from 6 to 200 and especially from 6 to 100.
Die Poly-C2-C4-Alkylenoxidgruppen Z der Monomere B weisen bevorzugt eine lineare oder verzweigte Struktur der Formeln (II.1) bzw. (II.2) auf:
-Z1-O-[Z2-O]n-R2 (II.1)
oder
- Z1, Z2 und Z3
- jeweils unabhängig voneinander für C2-C4-Alkandiyl stehen;
- Z4
- für C2-C4-Alkantriyl steht;
- n+1 bzw. m+k+1
- für eine ganze Zahl steht, wobei das Zahlenmittel von n+1 bzw. m+k+1 im Bereich von 4 bis 500, insbesondere von 6 bis 200 und speziell von 6 bis 100 liegt; und
- R2 und R3
- jeweils unabhängig voneinander für H, C1-C10-Alkyl oder Benzyl, vorzugsweise H oder C1-C4-Alkyl und speziell für C1-C2Alkyl stehen.
-Z 1 -O- [Z 2 -O] n -R 2 (II.1)
or
- Z 1 , Z 2 and Z 3
- each independently represent C 2 -C 4 alkanediyl;
- Z 4
- is C 2 -C 4 alkanetriyl;
- n + 1 and m + k + 1, respectively
- is an integer, wherein the number average of n + 1 and m + k + 1 is in the range of 4 to 500, especially 6 to 200 and especially 6 to 100; and
- R 2 and R 3
- each independently of one another are H, C 1 -C 10 -alkyl or benzyl, preferably H or C 1 -C 4 -alkyl and especially C 1 -C 2 -alkyl.
Hier und im Folgenden bedeutet Alkantriyl einen linearen oder verzweigten aliphatischen, dreibindigen, vorzugsweise über drei verschiedene C-Atome gebundenen Kohlenwasserstoffrest mit in der Regel 2 bis 4, insbesondere 3 C-Atomen.Here and below alkanetriyl means a linear or branched aliphatic, trivalent, preferably bonded via three different carbon atoms hydrocarbon radical having generally 2 to 4, in particular 3 C-atoms.
In den Formeln (II.1) und (II.2) stehen die Reste Z2 bzw. Z2 und Z3 bevorzugt für jeweils mindestens 50 %, besonders bevorzugt mindestens 75 % und ganz besonders bevorzugt etwa 100 % Ethylenoxid-Einheiten.In the formulas (II.1) and (II.2), the radicals Z 2 or Z 2 and Z 3 are preferably each at least 50%, more preferably at least 75% and most preferably about 100% ethylene oxide units.
In einer bevorzugten Ausführungsform stehen die Reste R2 und R3 in den Formeln (II.1) bzw. (II.2) jeweils unabhängig voneinander für Methyl.In a preferred embodiment, the radicals R 2 and R 3 in the formulas (II.1) and (II.2) are each independently of one another methyl.
Bevorzugt sind insbesondere Monomere B der Formel (I), worin Z für einen Rest der Formel (II.1) steht.Particular preference is given to monomers B of the formula (I) in which Z is a radical of the formula (II.1).
In einer weiteren bevorzugten Ausführungsform steht in Formel (I) die Variable X für H und Y für C(O)O oder C(O)NH. In dieser Ausführungsform steht die Variable Z in Formel (I) insbesondere für die vorstehend als bevorzugt genannten Strukturen der Formel (II.1) bzw. (II.2). R1 steht insbesondere für H oder Methyl. Besonders bevorzugt sind die Methylpoly-C2-C3-alkylenglykolester der Acrylsäure oder der Methacrylsäure und hierunter insbesondere solche mit einem Anteil von wenigstens 50 mol-%, insbesondere wenigstens 80 mol-% Ethylenoxid-Gruppen, jeweils bezogen auf die Gesamtmenge an C2-C3-Alkylenoxidgruppen, und speziell Methylpolyethylenglykolester der (Meth)Acrylsäure.In a further preferred embodiment, in formula (I) the variable X is H and Y is C (O) O or C (O) NH. In this embodiment, the variable Z in formula (I) is in particular the structures of the formula (II.1) or (II.2) mentioned above as being preferred. R 1 is in particular H or methyl. Particular preference is given to the methylpoly-C 2 -C 3 -alkylene glycol esters of acrylic acid or of methacrylic acid and, among these, especially those having a proportion of at least 50 mol%, in particular at least 80 mol% of ethylene oxide groups, in each case based on the total amount of C 2 C 3 alkylene oxide groups, and especially methyl polyethylene glycol esters of (meth) acrylic acid.
In einer weiteren bevorzugten Ausführungsform steht in Formel (I) die Variable X für H und Y für CH2-O. In dieser Ausführungsform steht die Variable Z in Formel (I) insbesondere für die vorstehend als bevorzugt genannten Strukturen der Formel (II.1) bzw. (II.2). R1 steht insbesondere für H oder Methyl. Besonders bevorzugt sind die Allylether-C2-C3-alkoxylate (R1 = H) und 2-Methylallyl-C2-C3-alkoxylate (R1 = Methyl), insbesondere solche mit endständiger Methylgruppe, und hierunter speziell solche mit einem Anteil von wenigstens 50 mol-%, insbesondere wenigstens 80 mol-% Ethylenoxid-Gruppen, jeweils bezogen auf die Gesamtmenge an C2-C3-Alkylenoxidgruppen, und ganz speziell Allyletherethoxylate (R1 = H).In a further preferred embodiment, in formula (I) the variable X is H and Y is CH 2 -O. In this embodiment, the variable Z in formula (I) is in particular the structures of the formula (II.1) or (II.2) mentioned above as being preferred. R 1 is in particular H or methyl. Particularly preferred are the allyl ether C 2 -C 3 alkoxylates (R 1 = H) and 2-methylallyl-C 2 -C 3 alkoxylates (R 1 = methyl), in particular those having a terminal methyl group, and especially those having a Proportion of at least 50 mol%, in particular at least 80 mol% of ethylene oxide groups, in each case based on the total amount of C 2 -C 3 alkylene oxide groups, and especially allyl ether ethoxylates (R 1 = H).
Die Monomere B können durch dem Fachmann bekannte Standardverfahren der organischen Chemie (siehe z. B.
Als Monomere B geeignete Allylalkoholpolyalkoxylate sind außerdem kommerziell erhältlich, z.B. unter den Namen Pluriol® A 010 R und Pluriol® A 11 RE von der BASF Aktiengesellschaft.Allyl alcohol polyalkoxylates suitable as monomers B are also commercially available, e.g. under the names Pluriol® A 010 R and Pluriol® A 11 RE from BASF Aktiengesellschaft.
Im Hinblick auf die farbübertragungsinhibierende Leistung der erfindungsgemäßen Copolymere in üblicherweise verwendeten Waschmitteln hat es sich als vorteilhaft erwiesen, wenn der Anteil der Monomere B höchstens 15 mol.% und insbesondere höchstens 10 mol.-% der Gesamtmenge der zur Herstellung der Copolymere eingesetzten Monomere ausmacht. Insbesondere beträgt der Anteil der Monomere B 0,5 bis 15 mol.-% und besonders bevorzugt 1 bis 10 mol.-%.With regard to the dye transfer-inhibiting performance of the copolymers of the invention in detergents commonly used, it has proved to be advantageous if the proportion of the monomers B at most 15 mol.% And especially at most 10 mol .-% of the total amount of the monomers used to prepare the copolymers. In particular, the proportion of the monomers B is 0.5 to 15 mol .-% and particularly preferably 1 to 10 mol .-%.
Neben den Monomeren A und B können die erfindungsgemäßen Copolymere ein oder mehrere weitere mit den Monomeren A und B copolymerisierbare Monomere C enthalten: Beispiele für Monomere C sind monoethylenisch ungesättigte C3-C10-Mono- und C4-C10-Dicarbonsäuren, z. B. (Meth)Acrylsäure, Crotonsäure, Fumarsäure und Maleinsäure; ethylenisch ungesättigte Sulfonsäuren und deren Salze, wie Vinylsulfonsäure, 2-Acryloxyethansulfonsäure, 2- und 3-Acryloxypropansulfonsäure, 2-Methyl-2-acrylamidopropansulfonsäure und Styrolsulfonsäure sowie deren Natriumsalze; Vinylester gesättigter C1-C10-Carbonsäuren, z. B. Vinylacetat und Vinylpropionat; Vinyl- und Allylether linearer oder verzweigter C1-C10-Alkohole, z. B. Vinylethylether, Vinylpropylether, Allylmethylether, Allylethylether und Allylpropylether; Vinylformamide, z. B. N-Vinyl-N-methylformamid und N-Vinylformamid selbst; die quaternären Produkte von N-Vinyl- und N-Allylaminen, wie alkylierte N-Vinyl- und N-Allylamine, z. B. N-Vinylmethylamin, N-Vinylethylamin, N-Allylmethylamin, N-Allylethylamin und N-Allylpropylamin; die Ester monoethylenisch ungesättigter C3-C6-Monocarbonsäuren oder C4-C6-Dicarbonsäuren mit linearen oder verzweigten aliphatischen C1-C10-Alkoholen, z. B. Acrylsäuremethylester, Acrylsäureethylester, Methacrylsäuremethylester, Methacrylsäureethylester, Maleinsäuredimethylester, Maleinsäurediethylester, 2-Ethylhexylacrylat und 2-Ethylhexylmethacrylat; die Halbester monoethylenisch ungesättigter C4-C6-Dicarbonsäuren mit linearen oder verzweigten C1-C10-Alkoholen, z. B. Maleinsäuremonomethylester und Maleinsäuremonoethylester; die Anhydride monoethylenisch ungesättigter C4-C6-Dicarbonsäuren, z. B. Maleinsäureanhydrid; Amide monoethylenisch ungesättigter C3-C6-Carbonsäuren mit primären und sekundären C1-C12-Aminen, z. B. (Meth)Acrylamid, N-Methyl(meth)acrylamid, N-Isopropyl(meth)-acrylamid oder N-butyl(meth)acrylamid; ungesättigte Nitrile, z. B. Acrylnitril und Methacrylnitril; und die Salze der genannten Säuren, die Derivate davon sowie deren Mischungen.In addition to the monomers A and B copolymers of the invention, one or more further with the A and B monomers copolymerizable monomers C include: Examples of monomers C are monoethylenically unsaturated C 3 -C 10 monocarboxylic and C 4 -C 10 dicarboxylic acids, e.g. , (Meth) acrylic acid, crotonic acid, fumaric acid and maleic acid; ethylenically unsaturated sulfonic acids and their salts, such as vinylsulfonic acid, 2-acryloxyethanesulfonic acid, 2- and 3-acryloxypropanesulfonic acid, 2-methyl-2-acrylamidopropanesulfonic acid and styrenesulfonic acid and their sodium salts; Vinyl esters of saturated C 1 -C 10 carboxylic acids, e.g. Vinyl acetate and vinyl propionate; Vinyl and allyl ethers of linear or branched C 1 -C 10 -alcohols, e.g. Vinyl ethyl ether, vinyl propyl ether, allyl methyl ether, allyl ethyl ether and allyl propyl ether; Vinylformamide, e.g. N-vinyl-N-methylformamide and N-vinylformamide itself; the quaternary products of N-vinyl and N-allylamines, such as alkylated N-vinyl and N-allylamines, e.g. N-vinylmethylamine, N-vinylethylamine, N-allylmethylamine, N-allylethylamine and N-allylpropylamine; the esters of monoethylenically unsaturated C 3 -C 6 -monocarboxylic acids or C 4 -C 6 -dicarboxylic acids with linear or branched aliphatic C 1 -C 10 -alcohols, for. Methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, dimethyl maleate, diethyl maleate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate; the half-esters of monoethylenically unsaturated C 4 -C 6 -dicarboxylic acids with linear or branched C 1 -C 10 -alcohols, eg. B. maleic acid monomethyl ester and maleic acid monoethyl ester; the anhydrides of monoethylenically unsaturated C 4 -C 6 dicarboxylic acids, eg. For example, maleic anhydride; Amides of monoethylenically unsaturated C 3 -C 6 carboxylic acids with primary and secondary C 1 -C 12 amines, eg. B. (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide or N-butyl (meth) acrylamide; unsaturated nitriles, e.g. For example, acrylonitrile and methacrylonitrile; and the salts of said acids, the derivatives thereof and mixtures thereof.
Die Anforderungen bestimmter Anwendungen können die Wahl der Art und Menge der Monomere C beeinflussen. So kann es wünschenswert sein, die erfindungsgemäßen Polymere vor einer Verwendung in selektiver Weise weiter umzusetzen, z. B. durch gezielte Alkoholyse, Aminolyse oder Hydrolyse. So können insbesondere Vinylalkoholeinheiten entsprechende Einheiten aus Vinylesterbausteinen und Vinylamineinheiten entsprechende Einheiten aus Vinylformamideinheiten gebildet werden.The requirements of certain applications may influence the choice of the type and amount of monomers C. Thus, it may be desirable to further react the polymers of the invention in a selective manner prior to use, e.g. As by targeted alcoholysis, aminolysis or hydrolysis. Thus, in particular vinyl alcohol units, corresponding units of vinyl ester units and units corresponding to vinylamine units can be formed from vinylformamide units.
In einer bevorzugten Ausführungsform ist das Monomer C ausgewählt unter monoethylenisch ungesättigten C3-C10-Mono- und C4-C10-Dicarbonsäuren, insbesondere Acrylsäure, Methacrylsäure und Maleinsäure.In a preferred embodiment, the monomer C is selected from monoethylenically unsaturated C 3 -C 10 -mono- and C 4 -C 10 -dicarboxylic acids, in particular acrylic acid, methacrylic acid and maleic acid.
In einer bevorzugten Ausführungsform beträgt der Anteil an Monomeren C weniger als 20 mol.-%, insbesondere weniger als 15 mol.-% und speziell weniger als 10 mol.-%, bezogen auf das Gesamtgewicht des Copolymers.In a preferred embodiment, the proportion of monomers C is less than 20 mol .-%, in particular less than 15 mol .-% and especially less than 10 mol .-%, based on the total weight of the copolymer.
In einer weiteren Ausführungsform beträgt der Anteil der Monomeren C 1 bis 20 mol.-%, insbesondere 1 bis 15 mol.-%, bezogen auf das Gesamtgewicht des Copolymers.In a further embodiment, the proportion of the monomers C is 1 to 20 mol .-%, in particular 1 to 15 mol .-%, based on the total weight of the copolymer.
Die K-Werte der erfindungsgemäß verwendeten Copolymere betragen üblicherweise 10 bis 150, bevorzugt 10 bis 80 und besonders bevorzugt 15 bis 60 (bestimmt nach
Die vorliegende Erfindung betrifft weiterhin ein Verfahren zur Herstellung der erfindungsgemäßen Copolymere, bei dem man das mindestens eine Monomer A mit dem mindestens einen Monomer B sowie gegebenenfalls mit den Monomeren C radikalisch polymerisiert.The present invention furthermore relates to a process for the preparation of the copolymers according to the invention in which the at least one monomer A is radically polymerized with the at least one monomer B and optionally with the monomers C.
Die radikalische Polymerisation der Monomere kann nach allen bekannten Methoden, wie Lösungspolymerisation, Emulsionspolymerisation, Suspensionspolymerisation oder Substanzpolymerisation, durchgeführt werden, bevorzugt sind die Verfahren der Lösungspolymerisation und der Substanzpolymerisation, ganz besonders bevorzugt die Lösungspolymerisation.The free-radical polymerization of the monomers can be carried out by any known method, such as solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization, preferably the methods of solution polymerization and bulk polymerization, very particularly preferably solution polymerization.
Vorteilhaft führt man eine Lösungspolymerisation in Wasser oder in Mischungen von Wasser mit organischen Lösungsmitteln als Reaktionsmedium durch. Es können jedoch auch organische Lösungsmittel(-gemische) allein als Reaktionsmedium verwendet werden.It is advantageous to carry out a solution polymerization in water or in mixtures of water with organic solvents as the reaction medium. However, organic solvents (mixtures) may also be used alone as the reaction medium.
Beispiele für geeignete organische Lösungsmittel sind aliphatische und cycloaliphatische einwertige C1-C4-Alkohole, z. B. Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, sec.-Butanol und tert.-Butanol; mehrwertige Alkohole, wie C1-C4-Glykole, z. B. Ethylenglykol, Propylenglykol und Butylenglykol und Glycerin; Mono- und Dialkylether mehrwertiger Alkohole, wie C1-C4-Alkylether der genannten mehrwertigen Alkohole, z. B. Monomethylethylenglykol, Monoethylethylenglykol, Dimethylethylenglykol und Dimethylpropylenglykol; Etheralkohole, z. B. Diethylenglykol und Triethylenglykol; sowie cyclische Ether, z. B. Dioxan. Bevorzugte organische Lösungsmittel sind Alkohole.Examples of suitable organic solvents are aliphatic and cycloaliphatic monohydric C 1 -C 4 -alcohols, e.g. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol; polyhydric alcohols, such as C 1 -C 4 -glycols, for. Ethylene glycol, propylene glycol and butylene glycol and glycerin; Mono- and dialkyl ethers of polyhydric alcohols, such as C 1 -C 4 -alkyl ethers of said polyhydric alcohols, eg. Monomethylethyleneglycol, monoethylethyleneglycol, dimethylethyleneglycol and dimethylpropyleneglycol; Ether alcohols, eg. For example, diethylene glycol and triethylene glycol; and cyclic ethers, e.g. Eg dioxane. Preferred organic solvents are alcohols.
Bevorzugt führt man die Polymerisation in einem wässrigen Polymerisationsmedium durch, das wenigstens 50 Vol-%, insbesondere wenigstens 80 Vol-% und besonders bevorzugt wenigstens 95 Vol-% Wasser, bezogen auf die Gesamtmenge an Lösungsmittel, enthält. Besonders bevorzugt führt man die Polymerisation in Wasser durch.The polymerization is preferably carried out in an aqueous polymerization medium which contains at least 50% by volume, in particular at least 80% by volume and particularly preferably at least 95% by volume of water, based on the total amount of solvent. Particularly preferably, the polymerization is carried out in water.
Sofern man die Lösungspolymerisation in einem wässrigen Polymerisationsmedium durchführt, wird vorzugsweise während der Polymerisation ein pH-Wert im Bereich von 2 bis 10, insbesondere von 3 bis 8 eingehalten.If the solution polymerization is carried out in an aqueous polymerization medium, a pH in the range from 2 to 10, in particular from 3 to 8, is preferably maintained during the polymerization.
Als Radikalstarter eignen sich insbesondere Peroxoverbindungen, Azoverbindungen, Redoxinitiatorsysteme und reduzierende Verbindungen. Selbstverständlich kann man auch Mischungen von Radikalstartern verwenden.Suitable radical initiators are, in particular, peroxo compounds, azo compounds, redox initiator systems and reducing compounds. Of course you can also use mixtures of radical starters.
Unter den thermisch aktivierbaren Polymerisationsinitiatoren sind Initiatoren mit einer Zerfallstemperatur ("10 h half-life decomposition temperature") im Bereich von 20 bis 180°C, insbesondere von 50 bis 120°C bevorzugt. Beispiele für bevorzugte thermische Initiatoren sind anorganische Peroxoverbindungen, wie Peroxodisulfate (Ammonium- und Alkalimetallsulfate, vorzugsweise Natriumperoxoxdisulfat), Peroxosulfate, Percarbonate und Wasserstoffperoxid; organische Peroxoverbindungen, wie Diacetylperoxid, Di-tert.-butylperoxid, Diamylperoxid, Dioctanoylperoxid, Didecanoylperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(o-toluyl)peroxid, Succinylperoxid, tert.-Butylperacetat, tert.-Butylpermaleinat, tert.-Butylperisobutyrat, tert.-Butylperpivalat, tert.-Butylperoctoat, tert.-Butylperneodecanoat, tert.-Butylperbenzoat, tert.-Butylperoxid, tert.-Butylhydroperoxid, Cumolhydroperoxid, tert.-Butylperoxi-2-ethylhexanoat und Diisopropylperoxidicarbamat; Azoverbindungen, wie 2,2'-Azobis-isobutyronitril, 2,2'-Azobis(2-methylbutyronitril) und Azobis(2-amidinopropan)dihydrochlorid.Among the thermally activatable polymerization initiators, preference is given to initiators having a decomposition temperature ("10 h half-life decomposition temperature") in the range from 20 to 180 ° C., in particular from 50 to 120 ° C. Examples of preferred thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and alkali metal sulfates, preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxy compounds, 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 permalate, tert-butyl perisobutyrate, tert. Butyl perpivalate, tert-butyl peroctoate, tert-butyl perodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate; Azo compounds such as 2,2'-azobis-isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidinopropane) dihydrochloride.
Diese Initiatoren können in Kombination mit reduzierenden Verbindungen als Starter/Regler-Systeme zum Einsatz kommen. Als Beispiele für derartige reduzierende Verbindungen seien phosphorhaltige Verbindungen, wie phosphorige Säure, Hypophosphite und Phosphinate, schwefelhaltige Verbindungen, wie Natriumhydrogensulfit, Natriumsulfit und Natriumformaldehydsulfoxilat, sowie Hydrazin genannt. Geeignet sind beispielsweise die Kombinationen tert-Butylhydroperoxid/Natriumdisulfit und tert-Butylhydroperoxid/Natriumhydroxymethansulfinat; des Weiteren Systeme mit Zusatz geringer Mengen von Redoxmetallsalzen wie Eisensalze, z.B. Ascorbinsäure/Eisen(II)sulfat/Natriumperoxodisulfat.These initiators can be used in combination with reducing compounds as starter / regulator systems. Examples of such reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine. Suitable examples are the combinations tert-butyl hydroperoxide / sodium disulfite and tert-butyl hydroperoxide / sodium hydroxymethanesulfinate; furthermore systems with addition small amounts of redox metal salts such as iron salts, eg ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.
Bevorzugte Initiatoren sind in der eingesetzten Menge im Polymerisationsmedium löslich. Daher sind besonders wasserlösliche Initiatoren bevorzugt. Besonders bevorzugte Initiatoren sind die vorgenannten Diazoverbindungen, insbesondere wasserlösliche Diazoverbindungen wie Azobis(2-amidinopropan)-dihydrochlorid.Preferred initiators are soluble in the amount used in the polymerization medium. Therefore, particularly water-soluble initiators are preferred. Particularly preferred initiators are the aforementioned diazo compounds, in particular water-soluble diazo compounds such as azobis (2-amidinopropane) dihydrochloride.
Ebenfalls geeignet sind Photoinitiatoren; z.B. Benzophenon, Acetophenon, Benzoinether, Benzyldialkylketone und deren Derivate.Also suitable are photoinitiators; e.g. Benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and their derivatives.
Die Polymerisationsinitiatoren werden je nach den Anforderungen des zu polymerisierenden Materials üblicherweise in Mengen von 0,01 bis 15 Gew.-%, vorzugsweise 0,25 bis 5 Gew.-%, jeweils bezogen auf die zu polymerisierenden Monomere, eingesetzt und können einzeln oder zur Ausnutzung vorteilhafter synergistischer Effekte in Kombination miteinander angewendet werden.Depending on the requirements of the material to be polymerized, the polymerization initiators are usually used in amounts of from 0.01 to 15% by weight, preferably from 0.25 to 5% by weight, based in each case on the monomers to be polymerized, and may be used singly or as Exploitation of beneficial synergistic effects in combination with each other.
Zur Begrenzung der Molmassen der erfindungsgemäßen Copolymere können bei der Polymerisation übliche Regler, z.B. Mercaptoverbindungen, wie Mercaptoethanol, Thioglycolsäure, 1,4-Bismercaptobutan-2,3-diol; Alkalimetallsulfite und -hydrogensulfite, wie Natriumsulfit; Alkalimetallphosphite und -hypophosphite, wie Natriumhypophosphit, etc. zugesetzt werden. Geeignete Mengen an Regler liegen im allgemeinen im Bereich von 0,01 bis 5 Gew.-%, bezogen auf die zu polymerisierenden Monomere.To limit the molecular weights of the copolymers according to the invention, it is possible to use regulators conventional in the polymerization, e.g. Mercapto compounds such as mercaptoethanol, thioglycolic acid, 1,4-bismercaptobutane-2,3-diol; Alkali metal sulfites and hydrogen sulfites such as sodium sulfite; Alkali metal phosphites and hypophosphites such as sodium hypophosphite, etc. are added. Suitable amounts of regulator are generally in the range of 0.01 to 5 wt .-%, based on the monomers to be polymerized.
Die Polymerisationstemperatur liegt in der Regel im Bereich von 10 bis 200°C, bevorzugt von 40 bis 140°C, besonders bevorzugt von 50 bis 120°C.The polymerization temperature is generally in the range from 10 to 200.degree. C., preferably from 40 to 140.degree. C., more preferably from 50 to 120.degree.
Die Polymerisation kann unter atmosphärischem Druck durchgeführt werden, gegebenenfalls kann sie auch in geschlossenem System unter dem sich entwickelnden Eigendruck vorgenommen werden.The polymerization may be carried out under atmospheric pressure, optionally it may also be carried out in a closed system under the evolving autogenous pressure.
Häufig schließt sich der Herstellung der Copolymere noch eine chemische und/oder physikalische Desodorierung, d. h. eine Entfernung nicht umgesetzter Monomere, an. Bei der physikalischen Desodorierung werden die Monomere mit Wasserdampf, z. B. durch Abdestillieren eines Teils des wässrigen Polymerisationsmediums und/oder mittels Durchleiten von Heißdampf, aus der Polymerisationsmischung entfernt. Bei der chemischen Desodorierung werden nicht umgesetzte Monomere in der Reaktionsmischung durch Anwendung verschärfter Polymerisationsbedingungen entfernt, z. B. durch Zugabe von weiterem Polymerisationsinitiator, häufig durch Zusatz der oben erwähnten Redoxinitiatoren und speziell durch Zusatz von Hydroperoxiden, wie Wasserstoffperoxid und Alkylhydroperoxiden, z. B. tert.-Butylhydroperoxid, in Kombination mit Reduktionsmitteln, insbesondere schwefelhaltigen Reduktionsmitteln, wie Hydrogensulfit, Dithionit, Addukte von Hydrogensulfit an Ketone, wie das Aceton-Bisulfit-Addukt, Hydroxymethansulfinat und dergleichen, gegebenenfalls in Anwesenheit von Spuren an Übergangsmetallen, z.B. Fe2+ oder Fe3+.Frequently, the production of the copolymers is followed by a chemical and / or physical deodorization, ie removal of unreacted monomers. In physical deodorization, the monomers are mixed with water vapor, e.g. B. by distilling off part of the aqueous polymerization medium and / or by passing superheated steam out of the polymerization mixture. In chemical deodorization, unreacted monomers in the reaction mixture are removed by use of more severe polymerization conditions, e.g. B. by the addition of further polymerization, often by addition of the above-mentioned redox initiators and especially by the addition of hydroperoxides, such as hydrogen peroxide and alkyl hydroperoxides, z. For example, tert-butyl hydroperoxide, in combination with reducing agents, in particular sulfur-containing reducing agents such as hydrogen sulfite, dithionite, adducts of bisulfite to ketones, such as the acetone-bisulfite adduct, hydroxymethanesulfinate and the like, optionally in the presence of traces of transition metals, eg Fe 2 + or Fe 3+ .
Alternativ zu dem beschriebenen Verfahren können die erfindungsgemäßen Copolymere auch erhalten werden, indem man die Poly-C2-C4-Alkylenoxidgruppen Z der Monomereinheiten B durch Polymer-analoge Umsetzung geeigneter, in einem Vorläufercopolymer enthaltener funktioneller Gruppen, die an die Monomereinheiten X-CH=CR1-der Monomere B gebunden sind, mit dem Vorläuferpolymer verknüpft. Als Polymer-analoge Umsetzung kommen z. B. die Aminierung, Umamidierung, Umesterung bzw. Alkoxylierung im Polymermolekül enthaltener (Meth)Acrylsäure-Einheiten, (Meth)Acrylsäureester-Einheiten, (Meth)Acrylamid-Einheiten sowie Maleinsäure-Einheiten, Maleinsäure(halb)ester-Einheiten, Maleinsäure(halb)amid-Einheiten, Vinylalkohol-Einheiten, Allylalkohol-Einheiten, Vinylamin-Einheiten und Allylamin-Einheiten, insbesondere die Polymer-analoge Veresterung und Amidierung von (Meth)Acrylsäure-Einheiten enthaltenden Vorläuferpolymeren in Betracht.As an alternative to the process described, the copolymers according to the invention can also be obtained by reacting the poly-C 2 -C 4 -alkylene oxide groups Z of the monomer units B by polymer-analogous reaction of suitable functional groups contained in a precursor copolymer to the monomer units X-CH = CR 1 -the monomers B are attached, linked to the precursor polymer. As polymer-analogous reaction z. As the amination, transamidation, transesterification or alkoxylation in the polymer molecule contained (meth) acrylic acid units, (meth) acrylic acid ester units, (meth) acrylamide units and maleic acid units, maleic acid (half) ester units, maleic acid (half ) amide units, vinyl alcohol units, allyl alcohol units, vinylamine units and allylamine units, in particular the polymer-analogous esterification and amidation of (meth) acrylic acid units containing precursor polymers into consideration.
Sollen dementsprechend die erfindungsgemäßen Copolymere auf (Meth)Acrylsäureestern oder -amiden als Komponenten der Monomereinheiten B basieren, kann man z. B. so vorgehen, dass man (Meth)Acrylsäure in einer zu der molaren Menge des Monomers B äquivalenten Menge mit dem Monomer A sowie gegebenenfalls dem Monomer C copolymerisiert und das gebildete Copolymer anschließend mit Polyalkylenglykolen, die nicht Endgruppen-verschlossen, einseitig durch Alkyl-, Phenyl- oder Alkylphenylreste Endgruppen-verschlossen bzw. einseitig aminiert oder einseitig durch Alkyl-, Phenyl- oder Alkylphenylreste Endgruppen-verschlossen und einseitig aminiert sind, verestert bzw. aminiert.Accordingly, should the copolymers of the invention based on (meth) acrylic acid esters or amides as components of the monomer units B, z. Example, proceed by copolymerizing (meth) acrylic acid in an amount equivalent to the molar amount of the monomer B with the monomer A and optionally the monomer C and then the copolymer formed with polyalkylene glycols which are not end-capped, unilaterally by alkyl , Phenyl or alkylphenyl radicals end-capped or aminated on one side or end-capped on one side by alkyl, phenyl or alkylphenyl radicals and aminated on one side, esterified or aminated.
Kommt als Monomer A ein Vinylpyridin-N-oxid zum Einsatz, so hat es sich als vorteilhaft erwiesen, zunächst die gewünschte Menge der entsprechenden Vinylpyridin-Verbindung mit den übrigen Monomeren zu copolymerisieren und anschließend das einpolymerisierte Vinylpyridin zu Vinylpyridin-N-oxid-Einheiten zu oxidieren.If a vinylpyridine N-oxide is used as monomer A, it has proven advantageous to first copolymerize the desired amount of the corresponding vinylpyridine compound with the other monomers and then to add the copolymerized vinylpyridine to vinylpyridine N-oxide units oxidize.
Die erfindungsgemäßen Copolymere eignen sich hervorragend als Farbstoffübertragungsinhibitoren beim Waschen von farbigen Textilien. Sie vermindern bzw. verhindern in wirksamer Weise eine Farbstoffübertragung zwischen den Textilien. Darüber hinaus sind sie universell in den verschiedensten Waschmitteln, wie flüssige und feste Waschmittel bzw. Waschmittelformulierungen, einsetzbar. Insbesondere weisen sie eine gute Verträglichkeit mit den üblichen Waschmittelkomponenten, speziell im Hinblick auf flüssige Waschmittel und Waschmittelformulierungen auf.The copolymers according to the invention are outstandingly suitable as dye transfer inhibitors in the washing of colored textiles. They effectively reduce or prevent dye transfer between the textiles. In addition, they can be used universally in a wide variety of detergents, such as liquid and solid detergents or detergent formulations. In particular, they have a good compatibility with the usual detergent components, especially with regard to liquid detergents and detergent formulations.
Eine gute Verträglichkeit bedeutet für die Zwecke der vorliegenden Erfindung, dass die erfindungsgemäßen Copolymere leicht in herkömmliche Komponenten enthaltende Waschmittelformulierungen eingearbeitet bzw. einformuliert werden können, ohne dass Entmischungsvorgänge auftreten, und dass die erhaltenen Waschmittel(-formulierungen) eine gute Stabilität, insbesondere gegenüber Entmischung, im Rahmen üblicher Standzeiten aufweise. Bei flüssigen Waschmittelformulierungen bedeutet dies insbesondere, dass vor und während der Verwendung keine signifikante Ausfällung der erfindungsgemäßen Copolymere stattfindet bzw. keine Trübungen auftreten.Good compatibility means, for the purposes of the present invention, that the copolymers according to the invention can easily be incorporated or formulated into detergent component formulations containing conventional components without segregation processes occurring, and that the resulting detergent formulations have good stability, in particular against segregation, within the usual life. In the case of liquid detergent formulations, this means, in particular, that no significant precipitation of the copolymers according to the invention takes place before or during use or turbidity does not occur.
Man nimmt an, dass die eine Farbübertragung inhibierende Wirkung der erfindungsgemäßen Copolymere auf die N-heterocyclischen Gruppen der Monomere A zurückzuführen ist. Demgegenüber wird im Hinblick auf die gute Verträglichkeit der erfindungsgemäßen Copolymere mit üblichen Waschmittelbestandteilen angenommen, dass diese auf die in den Monomeren B enthaltenen Alkylenoxid-Einheiten zurückzuführen ist. Dieser Effekt ist insbesondere deshalb überraschend, weil die aus dem Stand der Technik bekannten Pfropfpolymere (siehe z. B.
Die erfindungsgemäßen Copolymere werden in der Regel in Mengen im Bereich von 0,05 bis 5 Gew.-%, vorzugsweise 0,1 bis 2 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Waschmittel(-formulierungen), eingesetzt. Sie sind sowohl für Vollwaschmittel als auch für Spezialwaschmittel, wie Colorwaschmittel, geeignet. In farbschonenden Colorwaschmitteln kommen sie üblicherweise in Mengen im Bereich von 0,1 bis 1,5 Gew.-%, bevorzugt 0,1 bis 1 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Waschmittel(-formulierungen), zum Einsatz.The copolymers of the invention are generally used in amounts ranging from 0.05 to 5 wt .-%, preferably 0.1 to 2 wt .-%, each based on the total weight of the detergent (formulations). They are suitable for both heavy-duty detergents and special detergents, such as color detergents. In color-preserving color detergents, they are usually used in amounts ranging from 0.1 to 1.5% by weight, preferably 0.1 to 1% by weight, based in each case on the total weight of the detergents (formulations).
Die Waschmittel können in fester Form, z. B. in Pulver, Granulat-, Extrudat- oder Tablettenform, auch als sogenannte Kompaktwaschmittel mit einer Schüttdichte im Bereich von 500 bis 950 g/l, oder in flüssiger Einstellung vorliegen. Sie enthalten die üblicherweise verwendeten anionischen, nichtionischen und/oder kationischen Tenside in Mengen von 2 bis 50 Gew.-%, vorzugsweise 8 bis 30 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Waschmittel(-formulierungen). Besonders bevorzugt werden phosphatfreie oder phosphatreduzierte Waschmittel hergestellt, die einen Phosphatgehalt von höchstens 25 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Waschmittel-(formulierungen), berechnet als Pentanatriumtripolyphosphat, enthalten.The detergents can be in solid form, for. B. in powder, granule, extrudate or tablet form, as a so-called compact detergent with a bulk density in the range of 500 to 950 g / l, or in liquid setting. They contain the anionic, nonionic and / or cationic surfactants commonly used in amounts of 2 to 50 wt .-%, preferably 8 to 30 wt .-%, each based on the total weight of the detergent (formulations). Particular preference is given to producing phosphate-free or reduced-phosphate detergents which have a phosphate content of at most 25% by weight, based in each case on the total weight of the detergent formulations (formulations), calculated as pentasodium tripolyphosphate.
Geeignete anionische Tenside sind beispielsweise C8-C22-, vorzugsweise C10-C18-Fettalkoholsulfate, z.B. C9/C11-Alkoholsulfat, C12/C14-Alkoholsulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat.Suitable anionic surfactants are, for example, C 8 -C 22 , preferably C 10 -C 18, fatty alcohol sulfates, for example C 9 / C 11 -alcohol sulfate, C 12 / C 14 -alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.
Weitere geeignete anionische Tenside sind sulfatierte alkoxylierte C8-C22-, vorzugsweise C10-C18-Alkohole bzw. deren lösliche Salze. Verbindungen dieser Art werden beispielsweise dadurch hergestellt, daß man zunächst den Alkohol alkoxyliert und das Alkoxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man bevorzugt Ethylenoxid, wobei man pro mol Fettalkohol 2 bis 50 mol, insbesondere 3 bis 20 mol, Ethylenoxid einsetzt. Die Alkoxylierung kann jedoch auch mit Propylenoxid oder mit Butylenoxid durchgeführt werden. Selbstverständlich können die Alkylenoxide auch in Kombination zum Einsatz kommen. Die alkoxylierten Alkohole können die Ethylenoxid-, Propylenoxid- und/oder Butylenoxideinheiten dann in Form von Blöcken oder in statistischer Verteilung enthalten.Other suitable anionic surfactants are sulfated alkoxylated C 8 -C 22 -, preferably C 10 -C 18 -alcohols or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating the alcohol and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, with 2 to 50 mol, in particular 3 to 20 mol, of ethylene oxide being used per mole of fatty alcohol. However, the alkoxylation can also be carried out with propylene oxide or with butylene oxide. Of course, the alkylene oxides can also be used in combination. The alkoxylated alcohols may then contain the ethylene oxide, propylene oxide and / or butylene oxide units in the form of blocks or in random distribution.
Außerdem als anionische Tenside geeignet sind Alkylsulfonate, insbesondere C8-C24- und vor allem C10-C18-Alkylsulfonate, sowie Seifen, z.B. die Salze von aliphatischen C8-C24-Carbonsäuren.Also suitable as anionic surfactants are alkyl sulfonates, in particular C 8 -C 24 - and especially C 10 -C 18 -alkyl sulfonates, and soaps, for example the salts of aliphatic C 8 -C 24 -carboxylic acids.
Weitere geeignete anionische Tenside sind lineare C9-C20-Alkylbenzolsulfonate (LAS).Further suitable anionic surfactants are linear C 9 -C 20 -alkylbenzenesulfonates (LAS).
Die anionischen Tenside werden dem Waschmittel vorzugsweise in Form von Salzen zugegeben. Geeignete Kationen sind Alkalimetallionen, wie Natrium-, Kalium- und Lithiumionen, und Ammoniumionen, z.B. Hydroxyethylammonium-, Di(hydroxyethyl)-ammonium- und Tri(hydroxyethyl)ammoniumionen.The anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations are alkali metal ions, such as sodium, potassium and lithium ions, and ammonium ions, e.g. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium ions.
Als nichtionische Tenside eignen sich beispielsweise alkoxylierte C8-C22-, insbesondere C10-C18-Alkohole, wie Fettalkoholalkoxylate, Oxoalkoholalkoxylate und Guerbetalkoholalkoxylate. Die Alkoxylierung kann mit Ethylenoxid, Propylenoxid und/oder Butylenoxid durchgeführt werden. Die alkoxylierten Alkohole können die Alkylenoxideinheiten dann in Form von Blöcken oder in statistischer Verteilung enthalten. Pro mol Alkohol verwendet man 2 bis 50, vorzugsweise 3 bis 20 mol, mindestens eines dieser Alkylenoxide. Bevorzugt setzt man als Alkylenoxid Ethylenoxid ein.Examples of suitable nonionic surfactants are alkoxylated C 8 -C 22 -alcohols, in particular C 10 -C 18 -alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and guerbet alcohol alkoxylates. The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. The alkoxylated alcohols may then contain the alkylene oxide units in the form of blocks or in random distribution. From 2 to 50, preferably from 3 to 20, moles of at least one of these alkylene oxides are used per mole of alcohol. The alkylene oxide used is preferably ethylene oxide.
Weitere geeignete nichtionische Tenside sind Alkylphenolalkoxylate, insbesondere C6-C14-Alkylphenolethoxylate mit im Mittel 5 bis 30 Alkylenoxideinheiten enthalten.Further suitable nonionic surfactants are alkylphenol alkoxylates, in particular C 6 -C 14 -alkylphenol ethoxylates containing on average 5 to 30 alkylene oxide units.
Weitere geeignete nichtionische Tenside sind C8-C22-, insbesondere C10-C18-Alkylpolyglucoside. Diese Verbindungen enthalten 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten.Further suitable nonionic surfactants are C 8 -C 22 -, in particular C 10 -C 18 -alkylpolyglucosides. These compounds contain 1 to 20, preferably 1.1 to 5 glucoside units.
Eine weitere Klasse geeigneter nichtionischer Tenside sind N-Alkylglucamide der Strukturen (NT1) und (NT2):
Vorzugsweise enthalten die Waschmittelformulierungen mit 3 bis 12 mol Ethylenoxid ethoxylierte C10-C18-Alkohole als nichtionische Tenside.Preferably, the detergent formulations containing 3 to 12 moles of ethylene oxide ethoxylated C 10 -C 18 alcohols as nonionic surfactants.
Besonders geeignete kationische Tenside sind z.B. C7-C25-Alkylamine; C7-C25-N,N-Dimethyl-N-(hydroxyalkyl)ammoniumsalze; quaternisierte Mono- und Di-(C7-C25-)-alkyldimethylammoniumverbindungen; Esterquats, wie quaternäre veresterte Mono-, Di- oder Trialkanolamine, die mit C8-C22-Carbonsäuren verestert sind; und Imidazolinquats wie 1-Alkyl-imidazoliniumsalze der allgemeinen Formeln KT1 oder KT2:
Die pulverförmigen und granulatförmigen Waschmittel sowie gegebenenfalls auch strukturierte (mehrphasige) Flüssigwaschmittel enthalten außerdem einen oder mehrere anorganische Builder. Als anorganische Builder eignen sich dabei alle üblicherweise verwendeten Verbindungen, wie Alumosilikate, Silikate, Carbonate und Polyphosphate.The powdery and granular detergents and optionally also structured (multiphase) liquid detergents also contain one or more inorganic builders. Suitable inorganic builders are all commonly used compounds, such as aluminosilicates, silicates, carbonates and polyphosphates.
Als Beispiele seien im einzelnen kristalline und amorphe Alumosilikate mit ionenaustauschenden Eigenschaften, wie Zeolithe, z.B. Zeolith A, X, B, P, MAP und HS in ihrer Na-Form und in Formen, in denen Na teilweise gegen andere Kationen, wie Li, K, Ca, Mg oder Ammonium ausgetauscht ist, genannt.Specific examples are crystalline and amorphous aluminosilicates with ion-exchanging properties, such as zeolites, for example zeolite A, X, B, P, MAP and HS in their Na-form and in forms in which Na is partially exchanged for other cations, such as Li, K, Ca, Mg or ammonium.
Bei den Silikaten eignen sich z.B. amorphe und kristalline Silikate, wie amorphe Disilikate, Natriummetasilikat, kristalline Disilikate und Schichtsilikate, z.B. das Schichtsilikat SKS-6 (Clariant AG). Die Silikate können in Form ihrer Alkali-, Erdalkali- oder Ammoniumsalze eingesetzt werden. Vorzugsweise werden Na-, Li- und Mg-Silikate verwendet.For the silicates, e.g. amorphous and crystalline silicates such as amorphous disilicates, sodium metasilicate, crystalline disilicates and layered silicates, e.g. the layered silicate SKS-6 (Clariant AG). The silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Preferably, Na, Li and Mg silicates are used.
Als anorganische Builder geeignete Carbonate und Hydrogencarbonate können ebenfalls in Form ihrer Alkali-, Erdalkali- und Ammoniumsalze zum Einsatz kommen. Bevorzugt sind Na-, Li- und Mg-Carbonate und -Hydrogencarbonate, besonders bevorzugt sind Natriumcarbonat und/oder Natriumhydrogencarbonat. Als geeignetes Phosphat sei insbesondere Pentanatriumtriphosphat genannt.Carbonates and bicarbonates suitable as inorganic builders may also be used in the form of their alkali metal, alkaline earth metal and ammonium salts. Preference is given to sodium, lithium and magnesium carbonates and hydrogencarbonates, particular preference being given to sodium carbonate and / or sodium bicarbonate. As a suitable phosphate in particular pentasodium triphosphate called.
Die anorganischen Builder können in den Waschmitteln in Mengen von 5 bis 60 Gew.-% enthalten sein. Sie können allein oder in beliebigen Kombinationen miteinander in das Waschmittel eingearbeitet werden. In pulver- und granulatförmigen Waschmitteln werden sie in Mengen von 10 bis 60 Gew.-%, vorzugsweise 20 bis 50 Gew.-%, zugesetzt. In strukturierten Flüssigwaschmittein werden anorganische Builder in Mengen bis zu 40 Gew.-%, vorzugsweise bis zu 20 Gew.-%, eingesetzt. Sie werden dabei in den flüssigen Formulierungsbestandteilen suspendiert.The inorganic builders may be included in the detergents in amounts of from 5 to 60% by weight. They can be incorporated alone or in any combination with each other in the detergent. In powder and granular detergents, they are added in amounts of from 10 to 60% by weight, preferably from 20 to 50% by weight. In structured Flüssigwaschmittein inorganic builders in amounts up to 40 wt .-%, preferably up to 20 wt .-%, are used. They are suspended in the liquid formulation ingredients.
Die Waschmittel enthalten zusätzlich zu den anorganischen Buildern einen oder mehrere organische Cobuilder.The detergents contain one or more organic co-builders in addition to the inorganic builders.
Als organische Cobuilder eignen sich vor allem:
- Niedermolekulare Carbonsäuren, wie Citronensäure, hydrophob modifizierte Citronensäure, z. B. Agaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Oxyddibernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure, Alkyl- und Alkenylbernsteinsäuren und Aminopolycarbonsäuren, z.B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure.
- Oligomere und polymere Carbonsäuren, wie Homopolymere von Acrylsäure und Asparaginsäure, Oligomaleinsäuren, Copolymere der Maleinsäure mit Acrylsäure, Methacrylsäure oder C2-C22-Olefinen, z.B. Isobuten oder langkettigen α-Olefinen, Vinyl-C1-C3-alkylether, Vinylacetat, Vinylpropionat, (Meth)Acrylsäureester von C1-C8-Alkoholen und Styrol. Bevorzugt sind die Homopolymere der Acrylsäure und Copolymere von Acrylsäure mit Maleinsäure. Die oligomeren und polymeren Carbonsäuren werden in Säureform oder als Natriumsalz eingesetzt.
- Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, e.g. B. agaricic, malic, tartaric, gluconic, glutaric, succinic, imidodisuccinic, oxydisuccinic, propanetricarboxylic, butanetetracarboxylic, cyclopentanetetracarboxylic, alkyl- and alkenylsuccinic and aminopolycarboxylic, eg nitrilotriacetic acid, β-Alanindiessigsäure, ethylenediaminetetraacetic, Serindiessigsäure, Isoserindiessigsäure, N- (2-hydroxyethyl ) iminodiacetic acid, ethylenediamine disuccinic acid and methyl and ethylglycinediacetic acid.
- Oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or C 2 -C 22 -olefins, for example isobutene or long-chain α-olefins, vinyl-C 1 -C 3 -alkyl ethers, vinyl acetate, Vinyl propionate, (meth) acrylic acid esters of C 1 -C 8 -alcohols and styrene. Preferred are the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.
Die organischen Cobuilder sind in den pulver- und granulatförmigen sowie in den strukturierten flüssigen Waschmittelformulierungen in Mengen von 0,1 bis 15 Gew.-%, vorzugsweise 0,25 bis 8 Gew.-%, enthalten. In flüssigen Waschmittelformulierungen sind sie in Mengen von 0,1 bis 20 Gew.-% und bevorzugt 0,25 bis 10 Gew.-% enthalten.The organic co-builders are present in the powdered and granular as well as in the structured liquid detergent formulations in amounts of from 0.1 to 15% by weight, preferably from 0.25 to 8% by weight. In liquid detergent formulations, they are present in amounts of from 0.1 to 20% by weight and preferably from 0.25 to 10% by weight.
Die pulver- und granulatförmigen Vollwaschmittel können außerdem ein Bleichsystem, bestehend aus mindestens einem Bleichmittel, gegebenenfalls in Kombination mit einem Bleichaktivator und/oder einem Bleichkatalysator enthalten.The powdered and granular heavy-duty detergents may also contain a bleach system consisting of at least one bleach, optionally in combination with a bleach activator and / or a bleach catalyst.
Geeignete Bleichmittel sind beispielsweise Addukte von Wasserstoffperoxid an anorganische Salze, wie Natriumperborat-Monohydrat, Natriumperborat-Tetrahydrat und Natriumcarbonat-Perhydrat, sowie anorganische und organische Persäuren in Form ihrer Alkalimetall- oder Magnesiumsalze oder teilweise auch in Form der freien Säuren. Beispiele für geeignete organische Percarbonsäuren und deren Salze sind Mg-Monoperphthalat, Phthalimidopercapronsäure und Dodecan-1,10-dipersäure. Beispiel für ein anorganisches Persäuresalz ist K-Peroxomonosulfat (Oxon).Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, as well as inorganic and organic peracids in the form of their alkali metal or magnesium salts or partly also in the form of the free acids. Examples of suitable organic percarboxylic acids and their salts are Mg monoperphthalate, phthalimidopercaproic acid and dodecane-1,10-diacetic acid. An example of an inorganic peracid salt is K-peroxomonosulfate (oxone).
Falls Bleichmittel eingesetzt werden, so sind sie in Mengen von 5 bis 30 Gew.-%, vorzugsweise 10 bis 25 Gew.-%, in den Formulierungen enthalten.If bleaching agents are used, they are present in amounts of 5 to 30% by weight, preferably 10 to 25% by weight, in the formulations.
Als Bleichaktivatoren eignen sich z.B.: Acylamine, wie N,N,N',N'-Tetraacetylethylendiamin (TAED), Tetraacetylglycoluril, N,N'-Diacetyl-N,N'-dimethylharnstoff und 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin; acylierte Lactame, wie Acetylcaprolactam, Octanoylcaprolactam und Benzoylcaprolactam; substituierte Phenolester von Carbonsäuren, wie Na-Acetoxybenzolsulfonat, Na-Octanoyloxybenzolsulfonat und Natrium-p-nonanoyloxybenzolsulfonat; N-Methylmorpholiniumacetonitrilmethylsulfat und -hydrogensulfat; acylierte Zucker, wie Pentaacetylglucose; Anthranilderivate, wie 2-Methylanthranil und 2-Phenylanthranil; Enolester, wie Isopropenylacetat; Oximester, wie o-Acetylacetonoxim; darbonsäureanhydride, wie Phthalsäureanhydrid und Essigsäureanhydrid.Suitable bleach activators are, for example: acylamines, such as N, N, N ', N'-tetraacetylethylenediamine (TAED), tetraacetylglycoluril, N, N'-diacetyl-N, N'-dimethylurea and 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine; acylated lactams, such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam; substituted phenol esters of carboxylic acids such as Na-acetoxybenzenesulfonate, Na-octanoyloxybenzenesulfonate and sodium p-nonanoyloxybenzenesulfonate; N-Methylmorpholiniumacetonitrilmethylsulfat and hydrogen sulfate; acylated sugars, such as pentaacetylglucose; Anthranil derivatives such as 2-methylanthranil and 2-phenylanthranil; Enol esters, such as isopropenyl acetate; Oxime esters such as o-acetylacetone oxime; carboxylic acid anhydrides, such as phthalic anhydride and acetic anhydride.
Vorzugsweise werden Tetraacetylethylendiamin, Natrium-nonanoyloxybenzolsulfonate und N-Methylmorpholiniumacetonitrilmethylsulfat und -hydrogensulfat als Bleichaktivatoren eingesetzt.Preference is given to using tetraacetylethylenediamine, sodium nonanoyloxybenzenesulphonates and N-methylmorpholinium acetonitrile methylsulfate and hydrogensulfate as bleach activators.
Falls die Bleichaktivatoren in Waschmitteln eingesetzt werden, sind diese in Mengen von 0,1 bis 15 Gew.-%, vorzugsweise in Merigen von 1 bis 8 Gew.-%, besonders bevorzugt in Mengen von 1,5 bis 6 Gew.-% enthalten.If the bleach activators are used in detergents, they are present in amounts of from 0.1 to 15% by weight, preferably in amounts of from 1 to 8% by weight, more preferably in amounts of from 1.5 to 6% by weight ,
Geeignete Bleichkatalysatoren sind quaternisierte Imine und Sulfonimine und Mn- bzw. Co-Komplexe. Falls Bleichkatalysatoren in den Waschmittelformulierungen eingesetzt werden, sind sie in Mengen von bis zu 1,5 Gew.-%, vorzugsweise bis zu 0,5 Gew.-%, im Fall der sehr aktiven Mn-Komplexe in Mengen bis zu 0,1 Gew.-% enthalten.Suitable bleach catalysts are quaternized imines and sulfonimines and Mn or Co complexes. If bleach catalysts are used in the detergent formulations, they are in amounts of up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active Mn complexes in amounts up to 0.1% by weight .-% contain.
Die Waschmittel enthalten vorzugsweise ein Enzymsystem. Dabei handelt es sich üblicherweise um Proteasen, Lipasen, Amylasen oder Cellulasen. Das Enzymsystem kann auf ein einzelnes Enzym beschränkt sein oder eine Kombination verschiedener Enzyme beinhalten. Von den handelsüblichen Enzymen werden den Waschmitteln in der Regel Mengen von 0,1 bis 1,5 Gew.-%, vorzugsweise 0,2 bis 1 Gew.-%, des konfektionierten Enzyms zugesetzt. Geeignete Proteasen sind z.B. Savinase und Esperase (Hersteller Novo Nordisk), eine geeignete Lipase ist z.B. Lipolase (Hersteller Novo Nordisk), eine geeignete Cellulase ist z.B. Celluzym (Hersteller ebenfalls Novo Nordisk).The detergents preferably contain an enzyme system. These are usually proteases, lipases, amylases or cellulases. The enzyme system may be limited to a single enzyme or may include a combination of different enzymes. Of the commercial enzymes, the detergents are generally added amounts of 0.1 to 1.5 wt .-%, preferably 0.2 to 1 wt .-%, of the ready-made enzyme. Suitable proteases are e.g. Savinase and Esperase (manufactured by Novo Nordisk), a suitable lipase is e.g. Lipolase (manufactured by Novo Nordisk), a suitable cellulase is e.g. Celluzym (manufacturer also Novo Nordisk).
Die Waschmittel enthalten vorzugsweise außerdem Soil-Release-Polymere und/oder Vergrauungsinhibitoren. Dabei handelt es sich z.B. um Polyester aus einseitig mit zwei- und/oder mehrwertigen Alkoholen, insbesondere Ethylenglykol und/oder Propylenglykol, verschlossenen Polyethylenoxiden (Alkoholkomponente) und aromatischen Dicarbonsäuren oder aromatischen und aliphatischen Dicarbonsäuren (Säurekomponente). Weitere geeignete Soil-Release-Polymere sind amphiphile Pfropf- und Copolymerisate von Vinyl- und/oder Acrylestern auf bzw. mit Polyalkylenoxiden und modifizierte Cellulosen, z.B. Methylcellulose, Hydroxypropylcellulose und Carboxymethylcellulose.The detergents also preferably contain soil release polymers and / or grayness inhibitors. These are, for example, polyesters made from on one side with dihydric and / or polyhydric alcohols, in particular ethylene glycol and / or propylene glycol, closed polyethylene oxides (alcohol component) and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids (acid component). Further suitable soil-release polymers are amphiphilic graft copolymers and copolymers of vinyl and / or acrylic esters with or on polyalkylene oxides and modified celluloses, for example methylcellulose, hydroxypropylcellulose and carboxymethylcellulose.
Bevorzugt eingesetzte Soil-Release-Polymere sind Pfropfpolymerisate von Vinylacetat auf Polyethylenoxid des mittleren Molekulargewichts Mw 2500 bis 8 000 im Gewichtsverhältnis 1,2:1 bis 3:1, sowie handelsübliche Polyethylenterephthalat/Polyoxyethylenterephthalate des mittleren Molekulargewichts Mw 3000 bis 25000 aus Polyethylenoxiden des mittleren Molekulargewichts Mw 750 bis 5000 mit Terephthalsäure und Ethylenoxid und einem Molverhältnis von Polyethylenterephthalat zu Polyoxyethylenterephthalat von 8:1 bis 1:1 und Blockpolykondensate, die Blöcke aus (a) Ester-Einheiten aus Polyalkylenglykolen eines mittleren Molekulargewichts Mw von 500 bis 7500 und aliphatischen Dicarbonsäuren und/oder Monohydroxymonocarbonsäuren und (b) Ester-Einheiten aus aromatischen Dicarbonsäuren und mehrwertigen Alkoholen enthalten. Diese amphiphilen Blockpolymerisate haben mittlere Molekulargewichte Mw von 1500 bis 25000.Preferably used soil release polymers are graft polymers of vinyl acetate on polyethylene oxide of average molecular weight M w 2500 to 8 000 in a weight ratio of 1.2: 1 to 3: 1, and commercially available polyethylene terephthalate / polyoxyethylene terephthalates of average molecular weight M w 3000 to 25000 from polyethylene oxides of average molecular weight M w 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate of 8: 1 to 1: 1 and block polycondensates containing blocks of (a) ester units of polyalkylene glycols of average molecular weight M w from 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units of aromatic dicarboxylic acids and polyhydric alcohols. These amphiphilic block polymers have average molecular weights M w of 1500 to 25000.
Vergrauungsinhibitoren und Soil-Release-Polymere sind in den Waschmittetformutierungen in Mengen von 0 bis 2,5 Gew.-%, bevorzugt 0,2 bis 1,5 Gew.-%, besonders bevorzugt 0,3 bis 1,2 Gew.-%, enthalten.Grayness inhibitors and soil release polymers are in the detergent formulations in amounts of 0 to 2.5 wt .-%, preferably 0.2 to 1.5 wt .-%, particularly preferably 0.3 to 1.2 wt .-% , contain.
Ein weiterer Gegenstand der Erfindung ist eine feste Waschmittelformulierung, enthaltend
- a) 0,05 bis 5 Gew.-%, vorzugsweise 0,1 bis 2 Gew.-%, des erfindungsgemäßen farbübertragungsinhibierenden Copolymers;
- b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids;
- c) 0,5 bis 50 Gew.-% mindestens eines anorganischen Builders;
- d) 0 bis 10 Gew.-% mindestens eines organischen Cobuilders; und
- e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe wie Stellmittel, Enzyme, Parfüm, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, weitere Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Faser- und Farbschutzadditive, Silicone, Farbstoffe, Bakterizide, Auflösungsverbesserer und/oder Sprengmittel;
- a) 0.05 to 5 wt .-%, preferably 0.1 to 2 wt .-%, of the inventive color transfer inhibiting copolymer;
- b) from 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant;
- c) 0.5 to 50% by weight of at least one inorganic builder;
- d) 0 to 10% by weight of at least one organic cobuilder; and
- e) 0 to 60% by weight of other conventional ingredients such as setting agents, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, other color transfer inhibitors, grayness inhibitors, soil release polyesters, Fiber and color protective additives, silicones, dyes, bactericides, dissolution enhancers and / or disintegrants;
Gegenstand der Erfindung ist weiterhin eine flüssige Waschmittelformulierung enthaltend
- a) 0,05 bis 5 Gew.-%, vorzugsweise 0,1 bis 2 Gew.-%, des erfindungsgemäßen farbübertragungsinhibierenden Copolymers;
- b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids;
- c) 0 bis 20 Gew.-% mindestens eines anionischen Builders;
- d) 0 bis 10 Gew.-% mindestens eines organischen Cobuilders;
- e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe wie Soda, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, weitere Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Faser- und Farbschutzadditive, Silicone, Farbstoffe, Bakterizide, Löslichkeitsvermittler, Hydrotrope, Verdicker und/oder Alkanolamine; und
- f) 0 bis 99,45 Gew.-% Wasser, und/oder mehrwertige mit Wasser mischbare Alkohole, wie Monopropylenglycol, Dipropylenglycol und Glycerin, sowie Mischungen davon.
- a) 0.05 to 5 wt .-%, preferably 0.1 to 2 wt .-%, of the inventive color transfer inhibiting copolymer;
- b) from 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant;
- c) 0 to 20% by weight of at least one anionic builder;
- d) 0 to 10% by weight of at least one organic cobuilder;
- e) 0 to 60 wt .-% of other conventional ingredients such as soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, other color transfer inhibitors, grayness inhibitors, soil release polyester, fiber and color protective additives, silicones, dyes, bactericides , Solubilizers, hydrotropes, thickeners and / or alkanolamines; and
- f) 0 to 99.45% by weight of water, and / or polyhydric water-miscible alcohols, such as monopropylene glycol, dipropylene glycol and glycerol, and mixtures thereof.
Eine detaillierte Beschreibung der Waschmittelinhaltsstoffe findet man z. B. in der
Des Weiteren sind die erfindungsgemäßen Copolymere geeignet für die folgenden Anwendungen: Als Glanzbildner in Reinigungsmitteln, Hilfsmittel in der Textilherstellung, Hilfsmittel in kosmetischen Formulierungen, Adjuvans in Agroformulierungen, Additiv in der Wasserbehandlung, Hilfsmittel in Metallbearbeitungsmitteln und Kühlschmierstoffen sowie als Gashydratinhibitoren und bei anderen Anwendungsgebieten im Bereich Ölfeld.Furthermore, the copolymers according to the invention are suitable for the following applications: as brighteners in detergents, auxiliaries in textile production, adjuvants in cosmetic formulations, adjuvants in agrofuels, additives in water treatment, auxiliaries in metalworking agents and coolants and as gas hydrate inhibitors and in other fields of application oilfield.
Die folgenden Beispiele dienen der Erläuterung der Erfindung.The following examples serve to illustrate the invention.
In einem Reaktor wurden 800 g destilliertes Wasser unter Stickstoffzufuhr auf ca. 82°C (T) Innentemperatur erhitzt. Dann wurden 360 g Vinylpyrrolidon (VP) und parallel dazu eine Mischung von 20,8 g Methacrylsäure (MAS), 19,2 g α-Methoxy-ωmethacryloylpolyethylenglykol (mit einem zahlenmittleren Molekulargewicht des Polyethylenglykols (PEG) von ca. 1000) (MPEGMA) und 60 g Wasser (W1) innerhalb von 3 h kontinuierlich (d. h. mit gleich bleibender Geschwindigkeit) zudosiert. Gleichzeitig wurden innerhalb 4 h kontinuierlich 8 g 2,2'-Azobis(2-methylpropionamidin)-dihydrochlorid (V-50, Wako Chemicals) (V50) in 80 g Wasser (W2) zudosiert. Dann wurde eine weitere Stunde bei 82°C unter Stickstoffatmosphäre gerührt. Innerhalb von 30 min wurden 2 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid in 20 g Wasser zugegeben. Nach weiteren 2 h Rühren bei 82°C wurde die Lösung mit 50%iger wässriger Natronlauge auf einen pH-Wert von 7,2 eingestellt. Es wurde eine leicht gelbliche, klare Lösung mit einem Feststoffgehalt (F.G.) von 28 % und einem K-Wert (1 Gew.-% in wässriger Lösung) von 28,0 erhalten.In a reactor 800 g of distilled water were heated under nitrogen supply to about 82 ° C (T) internal temperature. Then, 360 g of vinylpyrrolidone (VP) and, in parallel, a mixture of 20.8 g of methacrylic acid (MAS), 19.2 g of α-methoxy-.omega.-methacryloylpolyethylene glycol (having a number-average molecular weight of polyethylene glycol (PEG) of about 1000) (MPEGMA). and 60 g of water (W1) within 3 h continuously (ie at a constant rate) added. At the same time, 8 g of 2,2'-azobis (2-methylpropionamidine) -dihydrochloride (V-50, Wako Chemicals) (V50) in 80 g of water (W2) were added continuously within 4 h. Then, stirring was continued for a further hour at 82 ° C under a nitrogen atmosphere. Within 30 minutes, 2 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride in 20 g of water were added. After a further 2 h stirring at 82 ° C, the solution was adjusted to a pH of 7.2 with 50% aqueous sodium hydroxide solution. A slightly yellowish, clear solution having a solids content (F.G.) of 28% and a K value (1% by weight in aqueous solution) of 28.0 was obtained.
Die Beispiele 2 bis 10 wurden analog Beispiel 1 durchgeführt, wobei jeweils die in Tabelle 1 unten angegebenen Mengen an Vinylpyrrolidon (VP), gegebenenfalls als Mischung mit der jeweils angegebenen Menge an Vinylimidazol (VI), sowie an Methacrylsäure (MAS), α-Metoxy-ω-methacryloylpolyethylenglykol (MPEGMA), Wasser (W1 und W2) bzw. 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid (V50) eingesetzt wurden.
In einem Reaktor wurden 385 g destilliertes Wasser und 80 g Allyletherethoxylat (Allylalkohol mit 10 Ethylenoxid(EO)-Einheiten) unter Stickstoffzufuhr auf 87°C (T) Innentemperatur erhitzt. Dann wurden 320 g Vinylpyrrolidon (VP) innerhalb von 3 h kontinuierlich zudosiert. Zeitlich um ca. 5 Minuten verschoben wurde eine Lösung von 6,4 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid (V50) in 58 g Wasser innerhalb von 3 h kontinuierlich zudosiert. Dann wurde eine weitere Stunde bei 87°C unter Stickstoffatmosphäre gerührt. Es wurde anschließend auf eine Innentemperatur von 60°C abgekühlt, dann wurden 2,3 g tert.-Butylhydroperoxid (70%ig), gelöst in 14 g Wasser (W3), auf einmal zugegeben. Anschließend wurden innerhalb von 30 Minuten 1,6 g Natriumdisulfit, gelöst in 50 g VE-Wasser, zugegeben. Der Ansatz wurde noch eine weitere Stunde bei 60°C gerührt. Es wurde eine leicht gelbliche, klare Lösung mit einem Feststoffgehalt von 46,2 % und einem K-Wert (1 Gew.-% in 3 Gew.-%iger wässriger NaCI-Lösung) von 33,7 erhalten.In a reactor, 385 g of distilled water and 80 g of allyl ether ethoxylate (allyl alcohol with 10 ethylene oxide (EO) units) were heated to 87 ° C (T) internal temperature while supplying nitrogen. Then, 320 g of vinylpyrrolidone (VP) were added continuously within 3 h. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water was added continuously within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C, then 2.3 g of tert-butyl hydroperoxide (70%), dissolved in 14 g of water (W3), added all at once. Then, within 30 minutes, 1.6 g of sodium bisulfite dissolved in 50 g of demineralized water were added. The mixture was stirred for a further hour at 60.degree. A slightly yellowish, clear solution having a solids content of 46.2% and a K value (1% by weight in 3% strength by weight aqueous NaCl solution) of 33.7 was obtained.
Die Beispiele 13, 15 und 16 wurden analog Beispiel 11 durchgeführt. Examples 13, 15 and 16 were carried out analogously to Example 11.
In einem Reaktor wurden 385 g dest. Wasser und 80 g Allyletherethoxylat (Allylalkohol mit 10 EO-Einheiten) unter Stickstoffzufuhr auf 87°C Innentemperatur erhitzt. Dann wurden 320 g Vinylpyrrolidon (VP) innerhalb von 2 h kontinuierlich zudosiert. Zeitlich um ca. 5 Minuten verschoben wurde eine Lösung von 6,4 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid (V50) in 58 g Wasser innerhalb von 2 h kontinuierlich zudosiert. Dann wurde eine weitere Stunde bei 87 °C unter Stickstoffatmosphäre gerührt. Es wurde anschließend auf eine Innentemperatur von 60°C abgekühlt; dann wurden 2,3 g tert.-Butylhydroperoxid (70%ig), gelöst in 14 g Wasser, auf einmal zugegeben. Anschließend wurden innerhalb von 30 Minuten 1,6 g Natriumdisulfit, gelöst in 50g VE-Wasser, zugegeben. Der Ansatz wurde noch eine weitere Stunde bei 60°C gerührt. Es wurde eine leicht gelbliche, klare Lösung mit einem Feststoffgehalt von 46,7 % und einem K-Wert (1 Gew.-% in 3 Gew.%iger NaCl-Lösung) von 36,7 erhalten.In a reactor 385 g were dist. Water and 80 g of allyl ether ethoxylate (allyl alcohol with 10 EO units) under nitrogen supply to 87 ° C internal temperature. Then, 320 g of vinylpyrrolidone (VP) were added continuously within 2 h. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water within 2 h continuously metered. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C; then 2.3 g of tert-butyl hydroperoxide (70%), dissolved in 14 g of water, were added all at once. Then, within 30 minutes, 1.6 g of sodium bisulfite dissolved in 50 g of demineralized water were added. The mixture was stirred for a further hour at 60.degree. A slightly yellowish, clear solution having a solids content of 46.7% and a K value (1% by weight in 3% strength by weight NaCl solution) of 36.7 was obtained.
Die Beispiele 14 und 17 wurden analog Beispiel 12 durchgeführt. Examples 14 and 17 were carried out analogously to Example 12.
In einem Reaktor wurden 385 g destilliertes Wasser und 80 g Allyletherethoxylat (Allylalkohol mit 16,6 EO-Einheiten) unter Stickstoffzufuhr auf 87°C (T) Innentemperatur erhitzt. Dann wurden zeitgleich 220 g Vinylpyrrolidon (VP) sowie 100 g Vinylimidazol (VI) innerhalb von 3 h kontinuierlich zudosiert. Zeitlich um ca. 5 Minuten verschoben wurde eine Lösung von 6,4 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid (V50) in 58 g Wasser innerhalb von 3 h kontinuierlich zudosiert. Dann wurde eine weitere Stunde bei 87°C unter Stickstoffatmosphäre gerührt. Es wurde eine leicht gelbliche, klare Lösung mit einem Feststoffgehalt von 48,7 % und einem K-Wert (1 Gew.-% in 3 Gew.-%iger wässriger NaCl-Lösung) von 41,5 erhalten.In a reactor, 385 g of distilled water and 80 g of allyl ether ethoxylate (16.6 EO allyl alcohol) were heated to 87 ° C (T) internal temperature with nitrogen. At the same time, 220 g of vinylpyrrolidone (VP) and 100 g of vinylimidazole (VI) were continuously metered in within 3 hours. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water was added continuously within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. A slightly yellowish, clear solution having a solids content of 48.7% and a K value (1% by weight in 3% strength by weight aqueous NaCl solution) of 41.5 was obtained.
Das Beispiel 19 wurde analog Beispiel 18 durchgeführt. Example 19 was carried out analogously to Example 18.
In einem Reaktor wurden 385 g dest. Wasser und 80 g Allyletherethoxylat (Allylalkohol mit 16,6 EO-Einheiten) unter Stickstoffzufuhr auf 87°C (T) Innentemperatur erhitzt. Dann wurden zeitgleich 220 g Vinylpyrrolidon (VP) sowie 100 g Vinylimidazol (VI) innerhalb von 3 h kontinuierlich zudosiert. Zeitlich um ca. 5 Minuten verschoben wurde eine Lösung von 6,4 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid (V50) in 58 g Wasser sowie eine weitere Lösung von 1,2 g Mercaptoethanol (ME), gelöst in 11 g Wasser, innerhalb von 3 h kontinuierlich zudosiert. Dann wurde eine weitere Stunde bei 87° C unter Stickstoffatmosphäre gerührt. Es wurde anschließend auf eine Innentemperatur von 60°C abgekühlt, dann wurden 2,3 g tert.-Butylhydroperoxid (70%ig), gelöst in 14 g Wasser, auf einmal zugegeben. Anschließend wurden innerhalb von 30 Minuten 1,6 g Natriumdisulfit, gelöst in 50 g VE-Wasser, zugegeben. Der Ansatz wurde noch eine weitere Stunde bei 60°C gerührt. Es wurde eine leicht gelbliche, klare Lösung mit einem Feststoffgehalt von 45,8% und einem K-Wert (1 Gew.-% in 3 Gew.-%iger wässriger NaCl-Lösung) von 34,4 erhalten.In a reactor 385 g were dist. Water and 80 g of allyl ether ethoxylate (allyl alcohol 16.6 EO units) under nitrogen to 87 ° C (T) internal temperature heated. At the same time, 220 g of vinylpyrrolidone (VP) and 100 g of vinylimidazole (VI) were continuously metered in within 3 hours. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water and a further solution of 1.2 g mercaptoethanol (ME), dissolved in 11 g of water, continuously added within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C, then 2.3 g of tert-butyl hydroperoxide (70%) dissolved in 14 g of water were added all at once. Then, within 30 minutes, 1.6 g of sodium bisulfite dissolved in 50 g of demineralized water were added. The mixture was stirred for a further hour at 60.degree. There was obtained a slightly yellowish, clear solution having a solids content of 45.8% and a K value (1 wt .-% in 3 wt .-% aqueous NaCl solution) of 34.4.
Das Beispiel 21 wurde analog Beispiel 20 durchgeführt. Example 21 was carried out analogously to Example 20.
In einem Reaktor wurden 385 g destilliertes Wasser und 80 g Allyletherethoxylat (Allylalkohol mit 16,6 EO-Einheiten) unter Stickstoffzufuhr auf 87°C Innentemperatur erhitzt. Dann wurden 320 g Vinylpyrrolidon (VP) innerhalb von 3 h kontinuierlich zudosiert. Zeitlich um ca. 5 Minuten verschoben wurde eine Lösung von 6,4 g 2,2'-Azobis(2-methylpropionamidin)dihydrochlorid (V50) in 58 g Wasser sowie eine weitere Lösung von 1,6 g Mercaptoethanol (ME), gelöst in 14,4 g Wasser, innerhalb von 3 h kontinuierlich zudosiert. Dann wurde eine weitere Stunde bei 87 °C unter Stickstoffatmosphäre gerührt. Es wurde anschließend auf eine Innentemperatur von 60°C abgekühlt; dann wurden 2,3 g tert.-Butylhydroperoxid (70%ig), gelöst in 14 g Wasser, auf einmal zugegeben. Anschließend wurden innerhalb von 30 Minuten 1,6 g Natriumdisulfit, gelöst in 50 g VE-Wasser, zugegeben. Der Ansatz wurde noch eine weitere Stunde bei 60°C gerührt. Es wurde eine leicht gelbliche, klare Lösung mit einem Feststoffgehalt von 32% und einem K-Wert (1 Gew.-% in 3 Gew.-%iger NaCl-Lösung) von 31 erhalten.In a reactor, 385 g of distilled water and 80 g of allyl ether ethoxylate (16.6 EO allyl alcohol) were heated to 87 ° C internal temperature with nitrogen. Then, 320 g of vinylpyrrolidone (VP) were added continuously within 3 h. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water and a further solution of 1.6 g of mercaptoethanol (ME), dissolved in 14.4 g of water, metered in continuously over 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C; then 2.3 g of tert-butyl hydroperoxide (70%), dissolved in 14 g of water, were added all at once. Then, within 30 minutes, 1.6 g of sodium bisulfite dissolved in 50 g of demineralized water were added. The mixture was stirred for a further hour at 60.degree. A slightly yellowish, clear solution having a solids content of 32% and a K value (1% by weight in 3% strength by weight NaCl solution) of 31 was obtained.
Das Beispiel 22 wurde analog Beispiel 23 durchgeführt, wobei jedoch kein Mercaptoethanol (ME) zudosiert wurde. Example 22 was carried out analogously to Example 23, but no mercaptoethanol (ME) was added.
In einem Reaktor wurden 385 g destilliertes Wasser und 80 g Allyletheralkoxylat (Allylalkohol mit 1 EO- und 42 Propylenoxid(PO)-Einheiten) unter Stickstoffzufuhr auf 87°C Innentemperatur erhitzt. Dann wurden zeitgleich 160 g Vinylpyrrolidon (VP) sowie 160 g Vinylimidazol (VI) innerhalb von 3 h kontinuierlich zudosiert. Zeitlich um ca. 5 Minuten verschoben wurde eine Lösung von 6,4 g 2,2'-Azobis(2-methylpropionamidin)-dihydrochlorid (V50) in 50 g Wasser innerhalb von 3 h kontinuierlich zudosiert. Dann wurde eine weitere Stunde bei 87°C unter Stickstoffatmosphäre gerührt. Es wurde anschließend auf eine Innentemperatur von 60°C abgekühlt; dann wurden 2,3 g tert.-Butylhydroperoxid (70%ig), gelöst in 14 g Wasser, auf einmal zugegeben. Anschließend werden innerhalb von 30 Minuten 9,6 g Natriumdisulfit, gelöst in 50 g VE-Wasser, zugegeben. Der Ansatz wurde noch eine weitere Stunde bei 60°C gerührt. Es wurde eine leicht gelbliche, klare Lösung mit einem Feststoffgehalt von 39,8% und einem K-Wert (1 Gew.-% in 3 Gew.-%iger NaCl-Lösung) von 40,5 erhalten.In a reactor, 385 g of distilled water and 80 g of allyl ether alkoxylate (allyl alcohol with 1 EO and 42 propylene oxide (PO) units) were heated to 87 ° C internal temperature with nitrogen. Then, at the same time, 160 g of vinylpyrrolidone (VP) and 160 g of vinylimidazole (VI) were metered in continuously over the course of 3 hours. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 50 g of water was added continuously within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C; then 2.3 g of tert-butyl hydroperoxide (70%), dissolved in 14 g of water, were added all at once. Subsequently, within 30 minutes, 9.6 g of sodium disulfite dissolved in 50 g of demineralized water was added. The mixture was stirred for a further hour at 60.degree. A slightly yellowish, clear solution having a solids content of 39.8% and a K value (1% by weight in 3% strength by weight NaCl solution) of 40.5 was obtained.
In einem Reaktor wurden 385 g destilliertes Wasser und 80 g Allyletheralkoxylat (Allylalkohol mit 1 EO- und 42 Propylenoxid(PO)-Einheiten) unter Stickstoffzufuhr auf 87°C (T) Innentemperatur erhitzt. Dann wurden 160 g Vinylpyrrolidon (VP) sowie parallei 160 g Vinylimidazol (VI) innerhalb von 3 h kontinuierlich zudosiert. Zeitlich um ca. 5 Minuten verschoben wurden je eine Lösung von 6,4 g 2,2'-Azobis(2-methylpropionamidin)-dihydrochlorid (V50) in 50 g Wasser sowie von 1,2 g Mercaptoethanol (ME) in 11 g destilliertem Wasser innerhalb von 3 h kontinuierlich zudosiert. Dann wurde eine weitere Stunde bei 87°C unter Stickstoffatmosphäre gerührt. Es wurde eine leicht gelbliche, klare Lösung mit einem Feststoffgehalt von 38,4 % und einem K-Wert (1 Gew.-% in 3 Gew.-%iger wässriger NaCl-Lösung) von 31,8 erhalten.In a reactor, 385 g of distilled water and 80 g of allyl ether alkoxylate (allyl alcohol with 1 EO and 42 propylene oxide (PO) units) were heated to 87 ° C (T) internal temperature with nitrogen. Then, 160 g of vinylpyrrolidone (VP) and parallei 160 g of vinylimidazole (VI) were added continuously within 3 h. Time shifted by about 5 minutes were each a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 50 g of water and 1.2 g of mercaptoethanol (ME) distilled in 11 g Water continuously added within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. A slightly yellowish, clear solution having a solids content of 38.4% and a K value (1% by weight in 3% strength by weight aqueous NaCl solution) of 31.8 was obtained.
In den nachstehenden Tabellen 2a und 2b sind die Parameter der Versuchsdurchführungen der Beispiele 11 bis 25 zusammengefasst.
Die erfindungsgemäßen Copolymere wurden als Farbübertragungsinhibitoren in Waschmitteln geprüft. Dafür wurden beispielhaft zwei granuläre Waschmittel (WM 1, WM2) und zwei Flüssigwaschmittel (WM 3, WM4) der in Tabelle 3 aufgeführten Zusammensetzungen hergestellt, wobei sich WM1 und WM2 bzw. WM3 und WM4 jeweils durch den Gehalt an erfindungsgemäßem Copolymer (WM1 = 0,15 Gew.-%; WM2 = 0,25 Gew.-%; WM3 = 0,15 Gew.-%; WM4 = 1 Gew.-%) unterschieden. Dann wurde weißes Baumwoll-Prüfgewebe unter den in Tabelle 4 genannten Waschbedingungen in Gegenwart von Farbstoff, der der Waschflotte als 0,03 bzw. 0,06 Gew.%ige wässrige Lösung zugesetzt wurde, gewaschen.The copolymers of the invention were tested as color transfer inhibitors in detergents. For this purpose, two granular detergents (WM 1, WM 2) and two liquid detergents (WM 3, WM 4) of the compositions listed in Table 3 were prepared by way of example, wherein WM 1 and WM 2 or WM 3 and WM 4 are in each case determined by the content of copolymer according to the invention (WM 1 = 0 , 15 wt%, WM2 = 0.25 wt%, WM3 = 0.15 wt%, WM4 = 1 wt%). Then it became white cotton test fabric under the washing conditions mentioned in Table 4 in the presence of dye which was added to the wash liquor as 0.03 or 0.06 wt.% Aqueous solution, washed.
Die Messung der Anfärbung des Prüfgewebes erfolgte photometrisch mit dem Photometer Elrepho 2000 (Datacolor). Die Remission (in %) wurde bei der Wellenlänge der jeweiligen maximalen Absorption der verschiedenen Farbstoffe gemessen. Der Weißgrad des Testgewebes nach der Wäsche diente zur Beurteilung der Anfärbung. Die in Tabelle 5 a - c angegebenen Messwerte wurden durch mehrfache Wiederholung und Mittelwertbildung gesichert.The staining of the test fabric was measured photometrically using the Elrepho 2000 photometer (Datacolor). The remission (in%) was measured at the wavelength of the respective maximum absorption of the different dyes. The whiteness of the test fabric after the wash was used to evaluate staining. The measured values given in Table 5 a - c were confirmed by multiple repetition and averaging.
In Tabelle 5 a - c sind die Ergebnisse der Waschversuche mit erfindungsgemäßen Copolymeren im Vergleich zu Waschversuchen ohne Farbstoffübertragungsinhibitor aufgeführt.
Die erhaltenen Waschergebnisse belegen die sehr gute Wirksamkeit der erfindungsgemäßen Copolymere als Farbübertragungsinhibitoren, die unabhängig von der Art des Farbstoffes ist.The washing results obtained show the very good effectiveness of the copolymers according to the invention as color transfer inhibitors, which is independent of the type of dye.
Zur Beurteilung der Stabilität der Copolymere in unterschiedlichen Flüssigwaschmittelformulierungen wurde jeweils 1 Gew.-% Copolymer in das Flüssigwaschmittel einformuliert und eine visuelle Beurteilung hinsichtlich Phasenseparation, Trübung, Inkompatibilitäten, usw. vorgenommen.In order to evaluate the stability of the copolymers in different liquid detergent formulations, 1% by weight of copolymer was in each case formulated in the liquid detergent and a visual assessment was carried out with regard to phase separation, turbidity, incompatibilities, etc.
Die Stablitätstests wurden mit der flüssigen Waschmittelformulierung WM4 durchgeführt.The stability tests were carried out with the liquid detergent formulation WM4.
In Tabelle 6 sind die visuellen Beurteilungen nach 4 Wochen Lagerung bei 40°C zusammengestellt.
Claims (18)
- The use of a copolymer comprising, in polymerized form,
(a) from 80 to 99.9 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer A which in each case comprises a heterocycle having at least 1 nitrogen atom and composed of from 3 to 10 ring members and a C2-C6-alkenyl group bonded to a carbon or nitrogen ring atom of the heterocycle; and (b)from 0.1 to 20 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer B copolymerizable with monomer A, said monomer B having a monoethylenically unsaturated double bond and also a linear or branched poly-C2-C4-alkylene oxide group having on average from 4 to 500 C2-C4-alkylene oxide units, - The use according to claim 1, wherein monomer A comprises at least one N-vinyllactam and, if appropriate, at least one N-vinylimidazole, and both the former and the latter may each have 1, 2, 3 or 4 substituents each independently selected from C1-C4-alkyl, C3-C6-cycloalkyl and phenyl.
- The use according to claim 2, wherein monomer A is selected from N-vinylpyrrolidone and mixtures of N-vinylpyrrolidone with N-vinylimidazole.
- The use according to any of the preceding claims, wherein the proportion of ethylene oxide units in monomer B is at least 50% based on the C2-C4-alkylene oxide units present in monomer B.
- The use according to any of the preceding claims, wherein the poly-C2-C4-alkylene oxide group in monomer B has 1 or 2 end groups which are each independently selected from H, C1-C10-alkyl and benzyl.
- The use according to claim 5, wherein the end groups are selected from C1-C2-alkyl.
- The use according to any of the preceding claims, wherein monomer B has the general formula I:
X-CH=CR1-Y-Z (I)
whereX is H or COOH;R1 is H or methyl;Y is O, CH2-O, C(O)O, C(O)NH, NHC(O) or CH2-NHC(O); andZ is a linear or branched poly-C2-C4-alkylene oxide group comprising on average from 4 to 500 C2-C4- alkylene oxide units and 1 or 2 terminal radicals each independently selected from H, C1- C10-alkyl and benzyl. - The use according to claim 7, wherein, in formula I, the variable X is H and Y is C(O)O or C(O)NH.
- The use according to claim 8, wherein the terminal radical(s) in Z is/are C1-C2-alkyl.
- The use according to any of the preceding claims, wherein monomer B is selected from the methyl polyethylene glycol esters of (meth)acrylic acid and allyl ether ethoxylates.
- The use according to claim 7, wherein, in formula I, the variable X is H and Y is CH2-O.
- The use according to any of the preceding claims, wherein the copolymer additionally comprises, in polymerized form, from 0 to 20 mol% of at least one monomer C copolymerizable with monomers A and B, said monomer C being selected from monoethylenically unsaturated C3-C10-mono- and -dicarboxylic acids, vinyl esters of saturated C1-C10-carboxylic acids, vinyl and allyl ethers of C1-C10-alcohols, vinylformamides, quaternary products of N-vinyl- and N-allylamines and derivatives thereof, and also mixtures thereof.
- The use according to any of the preceding claims, wherein the proportion of monomer C is at most 20 mol%.
- The use according to any of the preceding claims, wherein the copolymer has a K value in the range from 10 to 150.
- A copolymer comprising, in polymerized form,
(a) from 80 to 99.9 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer A which in each case comprises a heterocycle having at least 1 nitrogen atom and composed of from 3 to 10 ring members and a C2-C6-alkenyl group bonded to a carbon or nitrogen ring atom of the heterocycle; (b) from 0.1 to 20 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer B copolymerizable with monomer A, said monomer B having a monoethylenically unsaturated double bond and also a linear or branched poly- C2-C4-alkylene oxide group having on average from 4 to 500 C2-C4-alkylene oxide units, with the proviso that the end group of the poly-C2-C4-alkylene oxide group in the monomers B is selected from C1-C2-alkyl when monomer B is an ester of an ethylenically unsaturated carboxylic acid with a linear poly-C2-C4-alkylene oxide, and, if appropriate, (c) from 0 to 20 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer C copolymerizable with monomers A and B, - A process for preparing the copolymer according to claim 15, which comprises free-radically polymerizing the at least one monomer A with the at least one monomer B and also, if appropriate, with the monomers C.
- The process according to claim 16, wherein a solution polymerization is carried out in aqueous and/or alcoholic reaction medium.
- A liquid or solid detergent formulation comprising at least one copolymer as defined in any of claims 1 to 14, and customary washing substance
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JP2002206088A (en) * | 2000-11-08 | 2002-07-26 | Hitachi Maxell Ltd | Fluorescent complex and ink composition |
DE10059816C1 (en) * | 2000-12-01 | 2002-04-18 | Clariant Gmbh | Comb (co)polymers used as gas hydrate inhibitors, e.g. in petroleum and natural gas exploration, extraction, transport and storage, contain units derived from etherified di- or poly-oxyalkyl (alkyl)acrylate |
DE10156134A1 (en) | 2001-11-16 | 2003-05-28 | Basf Ag | Graft polymers with side chains containing cyclic N-vinylamides |
DE10156133A1 (en) | 2001-11-16 | 2003-05-28 | Basf Ag | Graft polymers with side chains containing nitrogen heterocycles |
DE10156135A1 (en) | 2001-11-16 | 2003-06-05 | Basf Ag | Graft polymers with side chains containing nitrogen heterocycles |
JP3879844B2 (en) * | 2001-12-26 | 2007-02-14 | ライオン株式会社 | Detergent antifouling composition and detersive antifouling article |
US20060229209A1 (en) | 2002-12-02 | 2006-10-12 | Lysander Chrisstoffels | Copolymers based on n-vinylamide as adjuvants and agents for using in the agrotechnical field |
-
2004
- 2004-04-27 DE DE102004020544A patent/DE102004020544A1/en not_active Withdrawn
-
2005
- 2005-04-26 AT AT05734132T patent/ATE423835T1/en not_active IP Right Cessation
- 2005-04-26 BR BRPI0510240A patent/BRPI0510240B1/en not_active IP Right Cessation
- 2005-04-26 ES ES05734132T patent/ES2321313T3/en active Active
- 2005-04-26 JP JP2007509958A patent/JP2007534816A/en active Pending
- 2005-04-26 EP EP05734132A patent/EP1743018B1/en not_active Not-in-force
- 2005-04-26 US US11/587,584 patent/US7728063B2/en not_active Expired - Fee Related
- 2005-04-26 CN CNB2005800136180A patent/CN100537736C/en not_active Expired - Fee Related
- 2005-04-26 MX MXPA06012026A patent/MXPA06012026A/en active IP Right Grant
- 2005-04-26 DE DE502005006696T patent/DE502005006696D1/en active Active
- 2005-04-26 CA CA002564812A patent/CA2564812A1/en not_active Abandoned
- 2005-04-26 WO PCT/EP2005/004467 patent/WO2005105968A1/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
JP2007534816A (en) | 2007-11-29 |
EP1743018A1 (en) | 2007-01-17 |
ES2321313T3 (en) | 2009-06-04 |
US7728063B2 (en) | 2010-06-01 |
ATE423835T1 (en) | 2009-03-15 |
DE502005006696D1 (en) | 2009-04-09 |
CN100537736C (en) | 2009-09-09 |
MXPA06012026A (en) | 2007-11-20 |
BRPI0510240B1 (en) | 2016-02-10 |
DE102004020544A1 (en) | 2005-11-24 |
US20070244023A1 (en) | 2007-10-18 |
BRPI0510240A (en) | 2007-10-23 |
CA2564812A1 (en) | 2005-11-10 |
CN1950493A (en) | 2007-04-18 |
WO2005105968A1 (en) | 2005-11-10 |
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