WO2019096590A1 - Detergent and cleaning agent with polymer active agent - Google Patents
Detergent and cleaning agent with polymer active agent Download PDFInfo
- Publication number
- WO2019096590A1 WO2019096590A1 PCT/EP2018/079971 EP2018079971W WO2019096590A1 WO 2019096590 A1 WO2019096590 A1 WO 2019096590A1 EP 2018079971 W EP2018079971 W EP 2018079971W WO 2019096590 A1 WO2019096590 A1 WO 2019096590A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylate
- acid
- carboxylic acid
- copolymer
- weight
- Prior art date
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- 239000003599 detergent Substances 0.000 title claims abstract description 27
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 title claims description 33
- 239000013543 active substance Substances 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims abstract description 50
- -1 carboxylic acids imides Chemical class 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 10
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 9
- 150000002825 nitriles Chemical class 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 150000003839 salts Chemical group 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 10
- 239000004753 textile Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 125000006239 protecting group Chemical group 0.000 claims description 4
- HUHXLHLWASNVDB-UHFFFAOYSA-N 2-(oxan-2-yloxy)oxane Chemical compound O1CCCCC1OC1OCCCC1 HUHXLHLWASNVDB-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001241 acetals Chemical class 0.000 claims description 3
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 3
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- CLHPBURJMZXHFZ-UHFFFAOYSA-N (1,2,2-trimethylcyclohexyl) prop-2-enoate Chemical compound CC1(C)CCCCC1(C)OC(=O)C=C CLHPBURJMZXHFZ-UHFFFAOYSA-N 0.000 claims description 2
- XPEMPJFPRCHICU-UHFFFAOYSA-N (1-tert-butylcyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C(C)(C)C)CCCCC1 XPEMPJFPRCHICU-UHFFFAOYSA-N 0.000 claims description 2
- BSSNZUFKXJJCBG-OWOJBTEDSA-N (e)-but-2-enediamide Chemical compound NC(=O)\C=C\C(N)=O BSSNZUFKXJJCBG-OWOJBTEDSA-N 0.000 claims description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 claims description 2
- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 claims description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 2
- KDAKDBASXBEFFK-UHFFFAOYSA-N 2-(tert-butylamino)ethyl prop-2-enoate Chemical compound CC(C)(C)NCCOC(=O)C=C KDAKDBASXBEFFK-UHFFFAOYSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 claims description 2
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000003857 carboxamides Chemical class 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- MCJIGEUBDWRFSC-UHFFFAOYSA-N n',n'-diethyl-2-methylidenebutanehydrazide Chemical compound CCN(CC)NC(=O)C(=C)CC MCJIGEUBDWRFSC-UHFFFAOYSA-N 0.000 claims description 2
- QTECWEOCNYGONE-UHFFFAOYSA-N n',n'-dimethyl-2-methylidenebutanehydrazide Chemical compound CCC(=C)C(=O)NN(C)C QTECWEOCNYGONE-UHFFFAOYSA-N 0.000 claims description 2
- DLJMSHXCPBXOKX-UHFFFAOYSA-N n,n-dibutylprop-2-enamide Chemical compound CCCCN(C(=O)C=C)CCCC DLJMSHXCPBXOKX-UHFFFAOYSA-N 0.000 claims description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 claims description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- RKSYJNCKPUDQET-UHFFFAOYSA-N n,n-dipropylprop-2-enamide Chemical compound CCCN(CCC)C(=O)C=C RKSYJNCKPUDQET-UHFFFAOYSA-N 0.000 claims description 2
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 claims description 2
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 claims description 2
- XQPVIMDDIXCFFS-UHFFFAOYSA-N n-dodecylprop-2-enamide Chemical compound CCCCCCCCCCCCNC(=O)C=C XQPVIMDDIXCFFS-UHFFFAOYSA-N 0.000 claims description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 2
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- CNWVYEGPPMQTKA-UHFFFAOYSA-N n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C=C CNWVYEGPPMQTKA-UHFFFAOYSA-N 0.000 claims description 2
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 claims description 2
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000701 coagulant Substances 0.000 claims 2
- 241001214176 Capros Species 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 claims 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 claims 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims 1
- 231100000719 pollutant Toxicity 0.000 claims 1
- 239000004519 grease Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 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 19
- 239000004480 active ingredient Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 150000002009 diols Chemical group 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 12
- 239000007844 bleaching agent Substances 0.000 description 12
- 239000000344 soap Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 102000004190 Enzymes Human genes 0.000 description 10
- 108090000790 Enzymes Proteins 0.000 description 10
- 229940088598 enzyme Drugs 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 7
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 7
- 239000004367 Lipase Substances 0.000 description 7
- 229920002125 Sokalan® Polymers 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003826 tablet Substances 0.000 description 7
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- 239000012190 activator Substances 0.000 description 6
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- FIBYGMZOYIOZGJ-UHFFFAOYSA-N (4-acetyloxy-5-ethenyloxolan-3-yl) acetate Chemical compound C(C)(=O)OC1C(OCC1OC(C)=O)C=C FIBYGMZOYIOZGJ-UHFFFAOYSA-N 0.000 description 5
- SGTGVDLNVPCDGO-UHFFFAOYSA-N 2-ethenyloxolane-3,4-diol Chemical compound C(=C)C1OCC(C1O)O SGTGVDLNVPCDGO-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
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- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 4
- 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 4
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- 230000002378 acidificating effect Effects 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
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- 150000001340 alkali metals Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 150000002338 glycosides Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
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- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
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- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical compound C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 3
- KZVAAIRBJJYZOW-UHFFFAOYSA-N 2-(hydroxymethyl)oxolane-3,4-diol Chemical compound OCC1OCC(O)C1O KZVAAIRBJJYZOW-UHFFFAOYSA-N 0.000 description 3
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/402—Alkyl substituted imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- 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
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- 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
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to certain monomers and polymers obtainable from renewable resources, to the use of such polymers for enhancing the primary detergency of laundry detergents or cleaners when washing textiles or cleaning hard surfaces, as well as detergents and cleaners containing such polymers.
- Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors.
- Such excipients also include substances whose presence enhances the detergency of surfactants, without them usually having to exhibit a pronounced surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces. Such substances are often referred to as Waschkraftverschreibr.
- copolymers have the disadvantage that they are essentially completely composed of monomers which are produced petrochemically. There is a need for laundry performance polymers that are at least partially composed of monomers that can be made from renewable resources.
- European Patent Application EP 3 009 430 A1 discloses that 2-vinyltetrahydrofuran-3,4-diol can be prepared from 1,4-sorbitan, 1,4-sorbitan from sorbitol and this from the renewable raw materials Glucose and fructose can be obtained.
- copolymers of ethylenically unsaturated carboxylic acids and ethylenically unsaturated monomers which can be prepared from sugar alcohols have particularly good properties which enhance the performance of detergents and cleaners.
- R 2 , R 3 and R 4 are the same;
- at least one of the radicals R 2 , R 3 and R 4 is hydrogen.
- Monomers of general formula I are accessible from sorbitol, xylitol or ribitol. They can be copolymerized in the presence of conventional free-radical initiators such as azobisisobutyronitrile or benzoyl peroxide with ethylenically unsaturated carboxylic acids or carboxylic acid derivatives, wherein the two hydroxyl groups in the polymerization by prior accumulation of conventional protecting groups, for example as acetal such as tetrahydropyranyl ether, as ketal such as acetonide or as a carboxylic acid ester such as acetate, can be protected and the protective groups removed after the polymerization again.
- conventional free-radical initiators such as azobisisobutyronitrile or benzoyl peroxide with ethylenically unsaturated carboxylic acids or carboxylic acid derivatives
- Another object of the invention are monomeric compounds of the general formula Ia,
- R 4 and R 2 , R 3 and R 4 independently of one another are H or an alkyl group having 1 to 3 C atoms, and derivatives thereof, in which the two hydroxyl groups are protected by raising customary protecting groups, for example as acetal such as tetrahydropyranyl ether, as ketal such as acetonide or as a carboxylic ester such as acetate.
- the a, b-monoethylenically unsaturated carboxylic acids and their derivatives mentioned are preferably selected from acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, esters such as dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, Butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, trimethylcyclohexyl acrylate, t-butylcyclohexyl acrylate, benzyl acrylate, hydroxyethyl acrylate, ethoxyethyl acrylate, ethoxyethoxyethyl acrylate, aminoethyl acrylate, t-but
- the copolymers according to the invention need not comprise carboxylic acid groups derived from the a, b-monoethylenically unsaturated monomer, carboxylic acid ester groups, carboxylic anhydride groups, carboxylic acid amide groups or carboxylic imide groups but these may be hydrolyzed in whole or at least partially in salt form, for example as sodium, potassium or ammonium carboxylate groups, wherein the ammonium group may also be substituted by 1 to 4 alkyl or hydroxyalkyl groups or mixtures thereof.
- the polymers essential to the invention are accessible as described by free-radical copolymerization of the stated monomers, which can be carried out as blockwise or preferably random copolymerization. They have no other units than units derived from the two monomers mentioned, it being possible for the units derived from the radical initiator or from the radical termination reaction to be present at the polymer ends as a result of the preparation.
- the units derived from the compound of the general formula I and the units derived from the a, b-monoethylenically unsaturated carboxylic acid and / or derivatives thereof are preferably in molar ratios in the range from 1: 1 to 1: 9, in particular 1: 1, 5 to 1: 5, before.
- the polymeric active ingredient preferably has an average molecular weight (here and below in the case of average molecular weight data: number average) in the range from 500 g / mol to 50,000 g / mol, in particular from 2000 g / mol to 10,000 g / mol.
- the use of the active ingredient according to the invention leads to a significantly better detachment of particular enzymatically or oxidatively removable stains on hard surfaces and textiles, including those made of cotton or with a share of cotton, as this is the case when using compounds previously known for this purpose.
- significant amounts of surfactants can be saved while retaining the ability to remove grease.
- the use according to the invention can be carried out in the context of a washing or cleaning process by adding the polymer essential to the invention to a washing or cleaning agent-containing aqueous liquor or preferably incorporating it as a constituent of a washing or cleaning agent into the liquor, the concentration of the active ingredient in the liquor
- the liquor is in the range of 0.004 g / l to 0.5 g / l, in particular from 0.01 g / l to 0.1 g / l.
- Another object of the invention is a method for removing in particular enzymatically or oxidatively removable soiling of textiles or hard surfaces by contacting the need for cleaning textile or hard surface requiring cleaning with an aqueous liquor, in which a detergent or cleaning agent and a named polymeric agent are located.
- This method can be carried out manually or mechanically, for example by means of a household washing machine or dishwasher. It is possible to use the particular liquid detergent or cleaning agent and the active ingredient simultaneously or sequentially. The simultaneous application can be carried out particularly advantageously by the use of an agent which contains the active ingredient.
- Enzymatically or oxidatively removable soilings are understood to mean those which are conventionally at least partially removed by the action of oxidizing agents, so-called bleaching agents, or by the action of enzymes in the washing or cleaning process.
- a further subject of the invention is therefore a washing or cleaning agent containing an above-defined inventive polymer.
- Detergents or cleaning agents which contain or are used together with an active substance to be used according to the invention or are used in the process according to the invention may contain all customary other constituents of such agents which do not interact in an undesired manner with the active ingredient essential to the invention.
- a polymeric agent as defined above in amounts of from 0.1 wt .-% to 10 wt .-%, in particular 0.3 wt .-% to 2 wt .-% incorporated in detergents or cleaning agents.
- An agent which contains an active ingredient to be used according to the invention or is used together or used in the process according to the invention preferably contains synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular alkylbenzenesulfonate, fatty alkylsulfate, fatty alkyl ether sulfate, alkyl and / or Dialkylsulfosuccinate, sulfo fatty acid esters and / or sulfo fatty acid, especially in an amount in the range of 2 wt .-% to 25 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%.
- These are usually not individual substances, but cuts or mixtures. Of these, preference is given to those whose content of compounds having longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.
- a further embodiment of such agents comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
- nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or
- Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms.
- the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
- Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
- alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
- suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
- the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettklarepolyhydroxyamide into consideration.
- alkylpolyglycosides which are suitable for incorporation in the agents according to the invention are compounds of the general formula (G) n - OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
- the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose.
- the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomermaschinesgrad.
- the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below one value of 1, 5, in particular between 1, 2 and 1, 4.
- Preferred monomer building block is glucose because of its good availability.
- Nonionic surfactant is present in compositions which contain an active ingredient used according to the invention or are used in the context of the use according to the invention, preferably in amounts of from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight. With amounts in the upper part of this range being more likely to be found in liquid detergents and particulate detergents preferably containing lower amounts of up to 5% by weight.
- the agents may instead or additionally contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type.
- Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are, in addition to the abovementioned alkylbenzenesulfonates, the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation call.
- Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols.
- the alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
- Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates.
- ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule.
- Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.
- Preferred anionic surfactants are also the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain Cs to Cis fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant.
- sulfosuccinates whose fatty alcohol residues are derive ethoxylated fatty alcohols with restricted homolog distribution, particularly preferred.
- soaps suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
- those soap mixtures are preferred which are composed of 50 wt .-% to 100 wt .-% of saturated Ci2-Ci8 fatty acid soaps and up to 50 wt .-% of oleic acid soap.
- soap is included in amounts of from 0.1% to 5% by weight.
- higher amounts of soap can be contained, usually up to 20 wt .-%.
- compositions may also contain betaine surfactants and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% to 7% by weight.
- betaine surfactants and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% to 7% by weight.
- esterquats discussed below are particularly preferred.
- the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activators, especially in amounts ranging from 2% to 10% by weight.
- the bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be in the form of tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts.
- Such bleaching agents are in detergents containing an active ingredient used in the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15% by weight and particularly preferably from 5 wt .-% to 15 wt .-%, respectively on total agent, present, in particular percarbonate is used.
- the optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phe- nolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammoniumacetonitrile salts.
- N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacety
- the bleach activators may have been coated and / or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or trial formulated in particulate form. kylammoniumacetonitrile is particularly preferred.
- Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
- the composition contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
- water-soluble and / or water-insoluble builder in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
- the agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
- the water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
- the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid ,
- a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to
- Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
- vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
- the acid content is at least 50% by weight.
- Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances.
- the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
- the second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred.
- the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. Particularly preferred are vinyl alcohol derivatives which are an ester of short chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol.
- Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate.
- the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives, is substituted.
- Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight. % to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or methallylsulfonate and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
- This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
- the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
- These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
- Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
- Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
- the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
- suitable aluminosilicates have no particles with a particle size greater than 30 ⁇ m and preferably consist of at least 80% by weight of particles having a size of less than 10 ⁇ m.
- Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates.
- the alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form.
- Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 0: Si0 2 of 1: 2 to 1: 2.8.
- Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those having a molar ratio of Na 2 O: SiO 2 of 1: 1, 9 to 1: 2.8 are preferably added as a solid and not in the form of a solution in the course of the preparation.
- the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Six0 2x + i yH 2 0 employed in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
- Crystalline layered silicates which fall under this general formula are described, for example, in European Patent Application EP 0 164 514.
- Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
- both ß- and d-sodium disilicates Na 2 Si 2 0s yH 2 0
- x is a number from 1, 9 to 2, 1
- a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda.
- Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention.
- the content of alkali metal silicates is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance.
- alkali metal aluminosilicate in particular zeolite
- the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
- the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1.
- the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2 : 1 and especially 1: 1 to 2: 1.
- water-soluble or water-insoluble inorganic substances may be contained in the agents containing an active ingredient to be used according to the present invention, used together with it or used in methods of the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.
- the agents may contain other ingredients customary in detergents or cleaners.
- these optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
- agents which are in accordance with the invention used active ingredient, up to 1 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% optical brightener, in particular compounds from the class of substituted 4,4'-bis (2,4, 6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for heavy metals, especially Aminoalkylenphosphonklaren and their Salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.
- optical brightener in particular compounds from the class of substituted 4,4'-bis (2,4, 6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up
- Solvents which can be used in particular for liquid agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.
- the active compounds used in the invention are usually dissolved or in suspended form.
- Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof.
- proteases derived from microorganisms such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms.
- Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
- the lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species.
- Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase.
- Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
- the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
- Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
- Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
- the customary enzyme stabilizers present, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali borates, boric acid-carboxylic acid combinations. NEN, boric acid esters, boronic acid derivatives, calcium salts, for example, Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.
- Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
- foam inhibitors are preferably bound to granular, water-soluble carrier substances.
- polyester-active soil release polymers which can be used in addition to the active compounds of the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
- dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
- diols for example ethylene glycol or propylene glycol
- polydiols for example polyethylene glycol or polypropylene glycol.
- Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
- Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
- R 11 denotes hydrogen
- a is a number from 2 to 6
- b is a number from 1 to 300.
- the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
- the degree of polymerization b is preferably in the range of 4 to 200, particularly 12 to 140.
- the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyester is in the range of 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol.
- the acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
- acids having at least two carboxyl groups may be included in the soil release-capable polyester.
- these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
- Preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms.
- R 11 is hydrogen and a is a number from 2 to 6
- R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms.
- those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
- diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
- Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.
- these polyesters composed as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
- the ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonklaren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based.
- valeric acid caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid , Arachinic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenz
- the end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which includes hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid.
- the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
- the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
- the soil release polymers are preferably water-soluble, the term "water-soluble” being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
- the preparation of solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later.
- a process comprising an extrusion step is preferred.
- compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
- the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN.
- a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
- the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
- the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
- Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
- Liquid or pasty compositions according to the invention in the form of customary solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
- an agent which is incorporated into the active ingredient to be used according to the invention is liquid and contains 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight, of nonionic surfactant, 2% by weight. % to 30% by weight, in particular 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular 2% by weight to 12.5% by weight of soap, 0, 5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1, 5 wt .-%, in particular 0.1 wt .-% to 1% by weight complexing agent for heavy metals, such as phosphonate, and in addition to optionally contained Enzyme, enzyme stabilizer, dye and / or fragrance water and / or water-miscible solvent.
- complexing agent for heavy metals such as phosphonate
- an agent in which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular from 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% by weight .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic Buder, up to 10 wt .-%, in particular 2 wt .-% to 8 Wt .-% of water-soluble organic Bu der, 10 wt .-% to 25 wt .-% synthetic anionic surfactant, 1 wt .-% to 5 wt .-% nonionic surfactant and up to 25 wt .-%, in particular 0.1 Wt .-% to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.
- bleaching agent in
- Test textiles provided with the standardized stains given in the table below were at 40 ° C. with a commercial bleach-free liquid detergent containing 5% by weight, based on the detergent, of one of the polymers prepared in Example 2 or, for comparison, the same amounts of the commercial one Polymer polyethylenimine (Sokalan® HP 20; V1) or polyacrylate (Acusol® 445N; V2) had been added, with a dosage of the detergent of 4, 1 g / l in tap water of 16 ° dH, washed. After washing with water and drying, the whiteness of the test textiles was determined spectrophotometrically (Minolta® CR400-1). In the following tables, the differences of the remission values (in each case in%) for the same use of the otherwise identically composed detergent without the polymer are given as mean values from 3 determinations.
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Abstract
The primary detergent power of detergent and cleaning agents is to be improved in particular with respect to soiling containing oil and/or grease. This is achieved substantially by incorporating copolymers which can be obtained by the copolymerization of compounds of the general formula (I), in which R1 represents -CR2=CR3R4 or -CH2-O-CH2-CR2=CR3R4 and R2, R3 and R4 independently of one another represent H or an alkyl group with 1 to 3 C atoms, α,ß-monoethylenically unsaturated carboxylic acids, carboxylic acid esters, carboxylic acid anhydrides, carboxylic acid amides, carboxylic acids imides, nitriles, and the mixtures thereof.
Description
Wasch- und Reinigungsmittel mit polymerem Wirkstoff Detergents and cleaning agents with polymeric agent
Die vorliegende Erfindung betrifft bestimmte aus nachwachsenden Rohstoffen zugängliche Monomere und Polymere, die Verwendung derartiger Polymere zur Verstärkung der Primärwaschkraft von Wasch- oder Reinigungsmitteln beim Waschen von Textilien oder Reinigen harter Oberflächen, sowie Wasch- und Reinigungsmittel, welche derartige Polymere enthalten. The present invention relates to certain monomers and polymers obtainable from renewable resources, to the use of such polymers for enhancing the primary detergency of laundry detergents or cleaners when washing textiles or cleaning hard surfaces, as well as detergents and cleaners containing such polymers.
Waschmittel enthalten neben den für den Waschprozess unverzichtbaren Inhaltsstoffen wie Tensiden und Buildermaterialien in der Regel weitere Bestandteile, die man unter dem Begriff Waschhilfsstoffe zusammenfassen kann und die so unterschiedliche Wirkstoffgruppen wie Schaumregulatoren, Vergrauungsinhibitoren, Bleichmittel, Bleichaktivatoren und Farbübertragungsinhibitoren umfassen. Zu derartigen Hilfsstoffen gehören auch Substanzen, deren Anwesenheit die Waschkraft von Tensiden verstärkt, ohne dass sie in der Regel selbst ein ausgeprägtes tensidisches Verhalten aufzuweisen müssen. Gleiches gilt sinngemäß auch für Reinigungsmittel für harte Oberflächen. Derartige Substanzen werden oft als Waschkraftverstärker bezeichnet. Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors. Such excipients also include substances whose presence enhances the detergency of surfactants, without them usually having to exhibit a pronounced surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces. Such substances are often referred to as Waschkraftverstärker.
Aus der internationalen Patentanmeldung WO 01/57171 A1 sind Wasch- oder Nachspülmittel bekannt, die neben Tensid Copolymere aus anionischen und kationischen Monomeren sowie gegebenenfalls zusätzlich nichtionischen Monomeren enthalten. International patent application WO 01/57171 A1 discloses washing or rinsing agents which, in addition to surfactant, comprise copolymers of anionic and cationic monomers and, if appropriate, additionally nonionic monomers.
Derartige Copolymere weisen den Nachteil auf, dass sie im Wesentlichen vollständig aus Monomeren aufgebaut sind, die petrochemisch erzeugt werden. Es besteht ein Bedarf nach waschleis- tungsfördernden Polymeren, die zumindest anteilig aus Monomeren aufgebaut sind, welche aus nachwachsenden Rohstoffen hergestellt werden können. Such copolymers have the disadvantage that they are essentially completely composed of monomers which are produced petrochemically. There is a need for laundry performance polymers that are at least partially composed of monomers that can be made from renewable resources.
Aus der Europäischen Patentanmeldung EP 3 009 430 A1 ist bekannt, dass 2-Vinyl-tetrahydro- furan-3,4-diol aus 1 ,4-Sorbitan hergestellt werden kann, wobei 1 ,4-Sorbitan aus Sorbitol und dieses aus den nachwachsenden Rohstoffen Glukose und Fruktose erhalten werden kann. European Patent Application EP 3 009 430 A1 discloses that 2-vinyltetrahydrofuran-3,4-diol can be prepared from 1,4-sorbitan, 1,4-sorbitan from sorbitol and this from the renewable raw materials Glucose and fructose can be obtained.
Überraschenderweise wurde gefunden, dass Copolymere aus ethylenisch ungesättigten Carbonsäuren und ethylenisch ungesättigten, aus Zuckeralkoholen herstellbaren Monomeren besonders gute die Leistung von Wasch- und Reinigungsmitteln verstärkende Eigenschaften haben. Surprisingly, it has been found that copolymers of ethylenically unsaturated carboxylic acids and ethylenically unsaturated monomers which can be prepared from sugar alcohols have particularly good properties which enhance the performance of detergents and cleaners.
Ein erster Gegenstand der Erfindung ist ein Copolymer, erhältlich durch radikalische Copolymerisation von Verbindungen der allgemeinen Formel I,
in der R1 für -CR2=CR3R4 oder -CH2-0-CH2-CR2=CR3R4 und R2, R3 und R4 unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen stehen, mit a,b-monoethylenisch ungesättigten Carbonsäuren, Carbonsäureestern, Carbonsäureanhydriden, Carbonsäureamiden, Carbonsäu- reimiden, Nitrilen und deren Mischungen. In bevorzugten Verbindungen der Formeln I sind R2, R3 und R4 gleich; in ebenfalls bevorzugten Verbindungen der Formel I ist mindestens einer der Reste R2, R3 und R4 Wasserstoff. A first subject of the invention is a copolymer obtainable by free-radical copolymerization of compounds of general formula I, in the R 1 for -CR 2 = CR 3 R 4 or -CH 2 -O-CH 2 -CR 2 = CR 3 R 4 and R 2 , R 3 and R 4 are independently H or an alkyl group having 1 to 3 C atoms are, with a, b-monoethylenically unsaturated carboxylic acids, carboxylic acid esters, carboxylic anhydrides, carboxylic acid amides, carboxylic imides, nitriles and mixtures thereof. In preferred compounds of formulas I, R 2 , R 3 and R 4 are the same; In likewise preferred compounds of the formula I, at least one of the radicals R 2 , R 3 and R 4 is hydrogen.
Monomere der allgemeinen Formel I sind aus Sorbitol, Xylitol oder Ribitol zugänglich. Sie können in Gegenwart üblicher Radikalstarter wie zum Beispiel Azobisisobutyronitril oder Benzoylperoxid mit ethylenisch ungesättigten Carbonsäuren oder Carbonsäurederivaten copolymerisiert werden, wobei die beiden Hydroxylgruppen bei der Polymerisation durch vorheriges Aufziehen üblicher Schutzgruppen, beispielsweise als Acetal wie Tetrahydropyranylether, als Ketal wie Acetonid oder als Carbonsäureester wie Acetat, geschützt werden können und man die Schutzgruppen nach der Polymerisation wieder entfernt. Monomers of general formula I are accessible from sorbitol, xylitol or ribitol. They can be copolymerized in the presence of conventional free-radical initiators such as azobisisobutyronitrile or benzoyl peroxide with ethylenically unsaturated carboxylic acids or carboxylic acid derivatives, wherein the two hydroxyl groups in the polymerization by prior accumulation of conventional protecting groups, for example as acetal such as tetrahydropyranyl ether, as ketal such as acetonide or as a carboxylic acid ester such as acetate, can be protected and the protective groups removed after the polymerization again.
Ein weiterer Gegenstand der Erfindung sind monomere Verbindungen der allgemeinen Formel la, Another object of the invention are monomeric compounds of the general formula Ia,
in der R1 für -CH2-0-CH2-CR2=CR3R4 und R2, R3 und R4 unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen stehen, sowie deren Derivate, bei denen die beiden Hydroxylgruppen durch Aufziehen üblicher Schutzgruppen, beispielsweise als Acetal wie Tetrahydropyranylether, als Ketal wie Acetonid oder als Carbonsäureester wie Acetat, geschützt sind. in which R 1 is -CH 2 -O-CH 2 -CR 2 = CR 3 R 4 and R 2 , R 3 and R 4 independently of one another are H or an alkyl group having 1 to 3 C atoms, and derivatives thereof, in which the two hydroxyl groups are protected by raising customary protecting groups, for example as acetal such as tetrahydropyranyl ether, as ketal such as acetonide or as a carboxylic ester such as acetate.
Die a,b-monoethylenisch ungesättigten Carbonsäuren und deren genannten Derivate werden vorzugsweise ausgewählt aus Säuren wie beispielsweise Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Estern wie beispielsweise Dimethylmaleat, Dieethylmaleat, Dimethylfumarat, Diethyl- fumarat, Methylacrylat, Ethylacrylat, n-Propylacrylat, Isopropylacrylat, Butylacrylat, Pentylacrylat, Hexylacrylat, 2-Ethylhexylacrylat, Nonylacrylat, Laurylacrylat, Trimethylcyclohexylacrylat, t-Butyl- cyclohexylacrylat, Benzylacrylat, Hydroxyethylacrylat, Ethoxyethylacrylat, Ethoxyethoxyethyl-
acrylat, Aminoethylacrylat, t-Butylaminoethylacrylat, N,N-Dimethylaminoethylacrylat, N,N-Diethyl- aminoethylacrylat, und entsprechende Methacrylate, Amiden wie beispielsweise Maleinsäuredi- amid, Fumarsäurediamid, Acrylamid, N-Methylacrylamid, N-Ethylacrylamid, N-n-Propylacrylamid, N-Isopropylacrylamid, N-Butylacrylamid, N-Octylacrylamid, N-Dodecylacrylamid, N-Octadecyl- acrylamid, N-Butoxymethylacrylamid, N,N-Dimethylacrylamid, N,N-Diethylacrylamid, N,N-Dipro- pylacrylamid, N,N-Dibutylacrylamid, N-(N‘,N‘-Dimethylamino)ethylacrylamid, N-(N‘,N‘-Diethyl- amino)ethylacrylamid, Methacrylamid und entsprechend N-substituierte Methacrylamide, Anhydriden wie beispielsweise Maleinsäureanhydrid, Imiden wie beispielsweise N-Acroyl- und N- Methacroylbutyro, -capro- und -valerolactam, Maleinimid, N-Phenyl- und N-Methyl-Maleinimid, Nitrilen wie beispielsweise Acetonitril und Fumarodinitril, die einzeln oder als Mischungen von zwei oder mehreren dieser Verbindungen eingesetzt werden können. The a, b-monoethylenically unsaturated carboxylic acids and their derivatives mentioned are preferably selected from acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, esters such as dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, Butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, trimethylcyclohexyl acrylate, t-butylcyclohexyl acrylate, benzyl acrylate, hydroxyethyl acrylate, ethoxyethyl acrylate, ethoxyethoxyethyl acrylate, aminoethyl acrylate, t-butylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, and corresponding methacrylates, amides such as maleic acid diamide, fumaric diamide, acrylamide, N-methylacrylamide, N-ethylacrylamide, Nn-propylacrylamide, N Isopropylacrylamide, N-butylacrylamide, N-octylacrylamide, N-dodecylacrylamide, N-octadecylacrylamide, N-butoxymethylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dipropylacrylamide, N, N-dibutylacrylamide , N- (N ', N'-dimethylamino) ethylacrylamide, N- (N', N'-diethylamino) ethylacrylamide, methacrylamide and correspondingly N-substituted methacrylamides, anhydrides such as maleic anhydride, imides such as N-acroyl and N-methacroylbutyro, -capro- and -valerolactam, maleimide, N-phenyl and N-methyl-maleimide, nitriles such as acetonitrile and fumarodinitrile, which may be used singly or as mixtures of two or more of these compounds.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der genannten Polymere zur Verstärkung der Primärwaschkraft von Wasch- oder Reinigungsmitteln beim Waschen von Textilien oder beim Reinigen harter Oberflächen gegenüber Anschmutzungen. Insbesondere in diesen müssen die erfindungsgemäßen Copolymere nicht aus dem a,b-monoethylenisch ungesättigten Monomer stammende Carbonsäuregruppen, Carbonsäureestergruppen, Carbonsäureanhydridgruppen, Carbonsäureamidgruppen oder Carbonsäureimidgruppen aufweisen, sondern diese können, ganz oder zumindest anteilig, hydrolysiert in Salzform, zum Beispiel als Natrium-, Kalium- oder Ammoni- umcarboxylatgruppen, vorliegen, wobei die Ammoniumgruppe auch mit 1 bis 4 Alkyl- oder Hy- droxyalkylgruppen oder deren Mischungen substituert sein kann. Another object of the invention is the use of said polymers to enhance the Primärwaschkraft of detergents or cleaning agents when washing textiles or when cleaning hard surfaces against stains. In particular in these, the copolymers according to the invention need not comprise carboxylic acid groups derived from the a, b-monoethylenically unsaturated monomer, carboxylic acid ester groups, carboxylic anhydride groups, carboxylic acid amide groups or carboxylic imide groups but these may be hydrolyzed in whole or at least partially in salt form, for example as sodium, potassium or ammonium carboxylate groups, wherein the ammonium group may also be substituted by 1 to 4 alkyl or hydroxyalkyl groups or mixtures thereof.
Die erfindungswesentlichen Polymere sind wie geschildert durch radikalische Copolymerisation der angegebenen Monomere, die als blockweise oder bevorzugt statistische Copolymerisation durchgeführt werden kann, zugänglich. Sie weisen außer aus den beiden genannten Monomeren stammenden Einheiten keine anderen Einheiten auf, wobei herstellungsbedingt an den Polymerenden aus dem Radikalstarter oder aus der Radikalabbruchreaktion stammende Einheiten anwesend sein können. The polymers essential to the invention are accessible as described by free-radical copolymerization of the stated monomers, which can be carried out as blockwise or preferably random copolymerization. They have no other units than units derived from the two monomers mentioned, it being possible for the units derived from the radical initiator or from the radical termination reaction to be present at the polymer ends as a result of the preparation.
Im erfindungswesentlichen Polymer liegen die aus der Verbindung der allgemeinen Formel I stammenden Einheiten und die aus der a,b-monoethylenisch ungesättigten Carbonsäure und/oder deren Derivaten stammenden Einheiten vorzugsweise in Molverhältnissen im Bereich von 1 :1 bis 1 :9, insbesondere von 1 :1 ,5 bis 1 :5, vor. Der polymere Wirkstoff weist vorzugsweise ein mittleres Molekulargewicht (hier und im Folgenden bei mittleren Molekulargewichtsangaben: Zahlenmittel) im Bereich von 500 g/mol bis 50000 g/mol, insbesondere von 2000 g/mol bis 10000 g/mol auf. In the polymer essential to the invention, the units derived from the compound of the general formula I and the units derived from the a, b-monoethylenically unsaturated carboxylic acid and / or derivatives thereof are preferably in molar ratios in the range from 1: 1 to 1: 9, in particular 1: 1, 5 to 1: 5, before. The polymeric active ingredient preferably has an average molecular weight (here and below in the case of average molecular weight data: number average) in the range from 500 g / mol to 50,000 g / mol, in particular from 2000 g / mol to 10,000 g / mol.
Der Einsatz des erfindungsgemäß verwendeten Wirkstoffs führt zu einer signifikant besseren Ablösung von insbesondere enzymatisch oder oxidativ entfernbaren Anschmutzungen auf harten Oberflächen und auf Textilien, auch solchen aus Baumwolle oder mit einem Anteil von Baumwolle, als
dies bei Verwendung bisher für diesen Zweck bekannter Verbindungen der Fall ist. Alternativ können bei gleich bleibendem Fettablösevermögen signifikante Mengen an Tensiden eingespart werden. The use of the active ingredient according to the invention leads to a significantly better detachment of particular enzymatically or oxidatively removable stains on hard surfaces and textiles, including those made of cotton or with a share of cotton, as this is the case when using compounds previously known for this purpose. Alternatively, significant amounts of surfactants can be saved while retaining the ability to remove grease.
Die erfindungsgemäße Verwendung kann im Rahmen eines Wasch- oder Reinigungsprozesses derart erfolgen, dass man das erfindungswesentliche Polymer einer wasch- oder reinigungsmittelhaltigen wässrigen Flotte zusetzt oder es vorzugsweise als Bestandteil eines Wasch- oder Reinigungsmittels in die Flotte einbringt, wobei die Konzentration an dem Wirkstoff in der Flotte vorzugsweise im Bereich von 0,004 g/l bis 0,5 g/l, insbesondere von 0,01 g/l bis 0,1 g/l liegt. The use according to the invention can be carried out in the context of a washing or cleaning process by adding the polymer essential to the invention to a washing or cleaning agent-containing aqueous liquor or preferably incorporating it as a constituent of a washing or cleaning agent into the liquor, the concentration of the active ingredient in the liquor Preferably, the liquor is in the range of 0.004 g / l to 0.5 g / l, in particular from 0.01 g / l to 0.1 g / l.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zum Entfernen von insbesondere enzymatisch oder oxidativ entfernbaren Anschmutzungen von Textilien oder harten Oberflächen durch Kontaktieren des reinigungsbedürftigen Textils oder der reinigungsbedürftigen harten Oberfläche mit einer wässrigen Flotte, in der sich ein Wasch- oder Reinigungsmittel und ein genannter polymerer Wirkstoff befinden. Dieses Verfahren kann manuell oder maschinell, zum Beispiel mit Hilfe einer Haushaltswaschmaschine oder Geschirrspülmaschine, ausgeführt werden. Dabei ist es möglich, das insbesondere flüssige Wasch- oder Reinigungsmittel und den Wirkstoff gleichzeitig oder nacheinander anzuwenden. Die gleichzeitige Anwendung lässt sich besonders vorteilhaft durch den Einsatz eines Mittels, welches den Wirkstoff enthält, durchführen. Unter enzymatisch oder oxidativ entfernbaren Anschmutzungen sollen dabei solche verstanden werden, die herkömlicherweise durch die Einwirkung von Oxidationsmitteln, sogenannten Bleichmitteln, oder durch die Einwirkung von Enzymen beim Wasch- oder Reinigungsprozess wenigstens teilweise entfernt werden. Another object of the invention is a method for removing in particular enzymatically or oxidatively removable soiling of textiles or hard surfaces by contacting the need for cleaning textile or hard surface requiring cleaning with an aqueous liquor, in which a detergent or cleaning agent and a named polymeric agent are located. This method can be carried out manually or mechanically, for example by means of a household washing machine or dishwasher. It is possible to use the particular liquid detergent or cleaning agent and the active ingredient simultaneously or sequentially. The simultaneous application can be carried out particularly advantageously by the use of an agent which contains the active ingredient. Enzymatically or oxidatively removable soilings are understood to mean those which are conventionally at least partially removed by the action of oxidizing agents, so-called bleaching agents, or by the action of enzymes in the washing or cleaning process.
Ein weiterer Gegenstand der Erfindung ist daher ein Wasch- oder Reinigungsmittel, enthaltend ein oben definiertes erfindungsgemäßes Polymer. A further subject of the invention is therefore a washing or cleaning agent containing an above-defined inventive polymer.
Wasch- oder Reinigungsmittel, die einen erfindungsgemäß zu verwendenden Wirkstoff enthalten oder mit diesem zusammen verwendet oder im erfindungsgemäßen Verfahren eingesetzt werden, können alle üblichen sonstigen Bestandteile derartiger Mittel enthalten, die nicht in unerwünschter Weise mit dem erfindungswesentlichen Wirkstoff wechselwirken. Vorzugsweise wird ein oben definierter polymerer Wirkstoff in Mengen von 0,1 Gew.-% bis 10 Gew.-%, insbesondere 0,3 Gew.-% bis 2 Gew.-% in Wasch- oder Reinigungsmittel eingearbeitet. Detergents or cleaning agents which contain or are used together with an active substance to be used according to the invention or are used in the process according to the invention may contain all customary other constituents of such agents which do not interact in an undesired manner with the active ingredient essential to the invention. Preferably, a polymeric agent as defined above in amounts of from 0.1 wt .-% to 10 wt .-%, in particular 0.3 wt .-% to 2 wt .-% incorporated in detergents or cleaning agents.
Ein Mittel, welches einen erfindungsgemäß zu verwendenden Wirkstoff enthält oder mit diesem zusammen verwendet wird oder im erfindungsgemäßen Verfahren zum Einsatz kommt, enthält vorzugsweise synthetisches Aniontensid vom Sulfat- und/oder Sulfonattyp, insbesondere Alkylben- zolsulfonat, Fettalkylsulfat, Fettalkylethersulfat, Alkyl- und/oder Dialkylsulfosuccinat, Sulfofettsäure- ester und/oder Sulfofettsäuredisalze, insbesondere in einer Menge im Bereich von 2 Gew.-% bis 25 Gew.-% und besonders bevorzugt von 5 Gew.-% bis 15 Gew.-%. Bevorzugt wird das Anionten-
sid aus den Alkylbenzolsulfonaten, den Alkyl- oder Alkenylsulfaten und/oder den Alkyl- oder Alke- nylethersulfaten ausgewählt, in denen die Alkyl- oder Alkenylgruppe 8 bis 22, insbesondere 12 bis 18 C-Atome besitzt. Bei diesen handelt es sich üblicherweise nicht um Einzelsubstanzen, sondern um Schnitte oder Mischungen. Darunter sind solche bevorzugt, deren Anteil an Verbindungen mit längerkettigen Resten im Bereich von 16 bis 18 C-Atomen über 20 Gew.-% beträgt. Besonders bevorzugt ist die Anwesenheit der oben genannten Kombination aus erfindungswesentlichem Polymer und Alkylbenzolsulfonat mit linearen C9-13-Alkylgruppen in den Mitteln. An agent which contains an active ingredient to be used according to the invention or is used together or used in the process according to the invention preferably contains synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular alkylbenzenesulfonate, fatty alkylsulfate, fatty alkyl ether sulfate, alkyl and / or Dialkylsulfosuccinate, sulfo fatty acid esters and / or sulfo fatty acid, especially in an amount in the range of 2 wt .-% to 25 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%. The anionic selected from the alkylbenzenesulfonates, the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. These are usually not individual substances, but cuts or mixtures. Of these, preference is given to those whose content of compounds having longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight. Particular preference is given to the presence of the abovementioned combination of polymer essential to the invention and alkylbenzenesulfonate with linear C 9-13 -alkyl groups in the agents.
Eine weitere Ausführungsform derartiger Mittel umfasst die Anwesenheit von nichtionischem Tensid, ausgewählt aus Fettalkylpolyglykosiden, Fettalkylpolyalkoxylaten, insbesondere -ethoxylaten und/oder -propoxylaten, Fettsäurepolyhydroxyamiden und/oder Ethoxylierungs- und/oder Propoxy- lierungsprodukten von Fettalkylaminen, vicinalen Diolen, Fettsäurealkylestern und/oder Fettsäureamiden sowie deren Mischungen, insbesondere in einer Menge im Bereich von 2 Gew.-% bis 25 Gew.-%. A further embodiment of such agents comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
Zu den in Frage kommenden nichtionischen Tensiden gehören die Alkoxylate, insbesondere die Ethoxylate und/oder Propoxylate von gesättigten oder ein- bis mehrfach ungesättigten linearen oder verzweigtkettigen Alkoholen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen. Der Alkoxylierungsgrad der Alkohole liegt dabei in der Regel zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Sie können in bekannter Weise durch Umsetzung der entsprechenden Alkohole mit den entsprechenden Alkylenoxiden hergestellt werden. Geeignet sind insbesondere die Derivate der Fettalkohole, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Alkoxylate eingesetzt werden können. Brauchbar sind demgemäß die Alkoxylate, insbesondere die Ethoxylate, primärer Alkohole mit linearen, insbesondere Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecyl-Resten sowie deren Gemische. Außerdem sind entsprechende Alkoxylierungsprodukte von Alkylaminen, vicinalen Diolen und Carbonsäureamiden, die hinsichtlich des Alkylteils den genannten Alkoholen entsprechen, verwendbar. Darüber hinaus kommen die Ethylenoxid- und/oder Propylenoxid-Insertionsprodukte von Fettsäurealkylestern sowie Fettsäurepolyhydroxyamide in Betracht. Zur Einarbeitung in die erfindungsgemäßen Mittel geeignete sogenannte Alkylpolyglykoside sind Verbindungen der allgemeinen Formel (G)n- OR12, in der R12 einen Alkyl- oder Alkenylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl zwischen 1 und 10 bedeuten. Bei der Glykosidkomponente (G)n handelt es sich um Oligo- oder Polymere aus natürlich vorkommenden Aldose- oder Ketose-Monomeren, zu denen insbesondere Glucose, Mannose, Fruktose, Galaktose, Talose, Gulose, Altrose, Allose, Idose, Ribose, Arabinose, Xylose und Lyxose gehören. Die aus derartigen glykosidisch verknüpften Monomeren bestehenden Oligomere werden außer durch die Art der in ihnen enthaltenen Zucker durch deren Anzahl, den sogenannten Oligomerisierungsgrad, charakterisiert. Der Oligomerisierungsgrad n nimmt als analytisch zu ermittelnde Größe im allgemeinen gebrochene Zahlenwerte an; er liegt bei Werten zwischen 1 und 10, bei den vorzugsweise eingesetzten Glykosiden unter einem Wert
von 1 ,5, insbesondere zwischen 1 ,2 und 1 ,4. Bevorzugter Monomer-Baustein ist wegen der guten Verfügbarkeit Glucose. Der Alkyl- oder Alkenylteil R12 der Glykoside stammt bevorzugt ebenfalls aus leicht zugänglichen Derivaten nachwachsender Rohstoffe, insbesondere aus Fettalkoholen, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Glykoside eingesetzt werden können. Brauchbar sind demgemäß insbesondere die primären Alkohole mit linearen Octyl-, Decyl-, Dodecyl-, Tetradecyl-, Hexadecyl- oder Octade- cylresten sowie deren Gemische. Besonders bevorzugte Alkylglykoside enthalten einen Kokosfettalkylrest, das heißt Mischungen mit im wesentlichen R12=Dodecyl und R12=Tetradecyl. Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettsäurepolyhydroxyamide into consideration. So-called alkylpolyglycosides which are suitable for incorporation in the agents according to the invention are compounds of the general formula (G) n - OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. The glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below one value of 1, 5, in particular between 1, 2 and 1, 4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R 12 of the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R 12 = dodecyl and R 12 = tetradecyl.
Nichtionisches Tensid ist in Mitteln, welche einen erfindungsgemäß verwendeten Wirkstoff enthalten oder im Rahmen der erfindungsgemäßen Verwendung eingesetzt werden, vorzugsweise in Mengen von 1 Gew.-% bis 30 Gew.-%, insbesondere von 1 Gew.-% bis 25 Gew.-% enthalten, wobei Mengen im oberen Teil dieses Bereiches eher in flüssigen Waschmitteln anzutreffen sind und teilchenförmige Waschmittel vorzugsweise eher geringere Mengen von bis zu 5 Gew.-% enthalten. Nonionic surfactant is present in compositions which contain an active ingredient used according to the invention or are used in the context of the use according to the invention, preferably in amounts of from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight. With amounts in the upper part of this range being more likely to be found in liquid detergents and particulate detergents preferably containing lower amounts of up to 5% by weight.
Die Mittel können stattdessen oder zusätzlich weitere Tenside, vorzugsweise synthetische Aniontenside des Sulfat- oder Sulfonat-Typs, enthalten. Als für den Einsatz in derartigen Mitteln besonders geeignete synthetische Aniontenside sind neben den bereits genannten Alkylbenzolsulfonaten die Alkyl- und/oder Alkenylsulfate mit 8 bis 22 C-Atomen, die ein Alkali-, Ammonium- oder Alkyloder Hydroxyalkyl-substituiertes Ammoniumion als Gegenkation tragen, zu nennen. Bevorzugt sind die Derivate der Fettalkohole mit insbesondere 12 bis 18 C-Atomen und deren verzweigtkettiger Analoga, der sogenannten Oxoalkohole. Die Alkyl- und Alkenylsulfate können in bekannter Weise durch Reaktion der entsprechenden Alkoholkomponente mit einem üblichen Sulfatierungsreagenz, insbesondere Schwefeltrioxid oder Chlorsulfonsäure, und anschließende Neutralisation mit Alkali-, Ammonium- oder Alkyl- oder Hydroxyalkyl-substituierten Ammoniumbasen hergestellt werden. Zu den einsetzbaren Tensiden vom Sulfat-Typ gehören auch die sulfatierten Alkoxylierungsprodukte der genannten Alkohole, sogenannte Ethersulfate. Vorzugsweise enthalten derartige Ethersulfate 2 bis 30, insbesondere 4 bis 10 Ethylenglykol-Gruppen pro Molekül. Zu den geeigneten Aniontensiden vom Sulfonat-Typ gehören die durch Umsetzung von Fettsäureestern mit Schwefeltrioxid und anschließender Neutralisation erhältlichen a-Sulfoester, insbesondere die sich von Fettsäuren mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, und linearen Alkoholen mit 1 bis 6 C-Atomen, vorzugsweise 1 bis 4 C-Atomen, ableitenden Sulfonierungsprodukte, sowie die durch formale Verseifung aus diesen hervorgehenden Sulfofettsäuren. Bevorzugte Aniontenside sind auch die Salze von Sulfobernsteinsäureestern, die auch als Alkylsulfosuccinate oder Dialkylsulfosuccinate bezeichnet werden, und die Monoester oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sul- fosuccinate enthalten Cs- bis C-is-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen ethoxylierten Fettalkoholrest, der für sich betrachtet ein nichtionisches Tenside darstellt. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich
von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. The agents may instead or additionally contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are, in addition to the abovementioned alkylbenzenesulfonates, the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation call. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids. Preferred anionic surfactants are also the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs to Cis fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant. Again, sulfosuccinates whose fatty alcohol residues are derive ethoxylated fatty alcohols with restricted homolog distribution, particularly preferred.
Als weitere fakultative tensidische Inhaltsstoffe kommen Seifen in Betracht, wobei gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure, sowie aus natürlichen Fettsäuregemischen, zum Beispiel Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifen geeignet sind. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 Gew.-% bis 100 Gew.-% aus gesättigten Ci2-Ci8-Fettsäureseifen und zu bis 50 Gew.-% aus Ölsäureseife zusammengesetzt sind. Vorzugsweise ist Seife in Mengen von 0,1 Gew.-% bis 5 Gew.-% enthalten. Insbesondere in flüssigen Mitteln, welche einen erfindungsgemäß verwendeten Wirkstoff enthalten, können jedoch auch höhere Seifenmengen von in der Regel bis zu 20 Gew.-% enthalten sein. Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 wt .-% to 100 wt .-% of saturated Ci2-Ci8 fatty acid soaps and up to 50 wt .-% of oleic acid soap. Preferably, soap is included in amounts of from 0.1% to 5% by weight. In particular, in liquid agents containing an active ingredient according to the invention, however, higher amounts of soap can be contained, usually up to 20 wt .-%.
Gewünschtenfalls können die Mittel auch Betaintenside und/oder kationische Tenside enthalten, die - falls vorhanden - vorzugsweise in Mengen von 0,5 Gew.-% bis 7 Gew.-% eingesetzt werden. Unter diesen sind die unten diskutierten Esterquats besonders bevorzugt. If desired, the compositions may also contain betaine surfactants and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% to 7% by weight. Among them, the esterquats discussed below are particularly preferred.
Die Mittel können gewünschtenfalls Bleichmittel auf Persauerstoffbasis, insbesondere in Mengen im Bereich von 5 Gew.-% bis 70 Gew.-%, sowie gegebenenfalls Bleichaktivator, insbesondere in Mengen im Bereich von 2 Gew.-% bis 10 Gew.-%, enthalten. Die in Betracht kommenden Bleichmittel sind vorzugsweise die in Waschmitteln in der Regel verwendeten Persauerstoffverbindungen wie Percarbonsäuren, beispielsweise Dodecandipersäure oder Phthaloylaminoperoxicapronsäure, Wasserstoffperoxid, Alkaliperborat, das als Tetra- oder Monohydrat vorliegen kann, Percarbonat, Perpyrophosphat und Persilikat, die in der Regel als Alkalisalze, insbesondere als Natriumsalze, vorliegen. Derartige Bleichmittel sind in Waschmitteln, welche einen erfindungsgemäß verwendeten Wirkstoff enthalten, vorzugsweise in Mengen bis zu 25 Gew.-%, insbesondere bis zu 15 Gew.- % und besonders bevorzugt von 5 Gew.-% bis 15 Gew.-%, jeweils bezogen auf gesamtes Mittel, vorhanden, wobei insbesondere Percarbonat zum Einsatz kommt. Die fakultativ vorhandene Komponente der Bleichaktivatoren umfasst die üblicherweise verwendeten N- oder O-Acylverbindun- gen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-isononanoyl-phe- nolsulfonat, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose, sowie kationische Nitrilderivate wie Trimethylammoniumacetonitril-Salze. Die Bleichaktivatoren können zur Vermeidung der Wechselwirkung mit den Perverbindungen bei der Lagerung in bekannter Weise mit Hüllsubstanzen überzogen und/oder granuliert worden sein, wobei mit Hilfe von Carboxymethylcellulose granuliertes Tetraacetylethylendiamin mit mittleren Korngrößen von 0,01 mm bis 0,8 mm, granuliertes 1 ,5-Diacetyl-2,4-dioxohexahydro-1 ,3,5-triazin, und/oder in Teilchenform konfektioniertes Trial-
kylammoniumacetonitril besonders bevorzugt ist. In Waschmitteln sind derartige Bleichaktivatoren vorzugsweise in Mengen bis zu 8 Gew.-%, insbesondere von 2 Gew.-% bis 6 Gew.-%, jeweils bezogen auf gesamtes Mittel, enthalten. If desired, the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activators, especially in amounts ranging from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be in the form of tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents containing an active ingredient used in the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15% by weight and particularly preferably from 5 wt .-% to 15 wt .-%, respectively on total agent, present, in particular percarbonate is used. The optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phe- nolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. The bleach activators may have been coated and / or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or trial formulated in particulate form. kylammoniumacetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
In einer weiteren Ausführungsform enthält das Mittel wasserlöslichen und/oder wasserunlöslichen Builder, insbesondere ausgewählt aus Alkalialumosilikat, kristallinem Alkalisilikat mit Modul über 1 , monomerem Polycarboxylat, polymerem Polycarboxylat und deren Mischungen, insbesondere in Mengen im Bereich von 2,5 Gew.-% bis 60 Gew.-%. In a further embodiment, the composition contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
Das Mittel enthält vorzugsweise 20 Gew.-% bis 55 Gew.-% wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Builder- substanzen gehören insbesondere solche aus der Klasse der Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, sowie der polymeren (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden zugänglichen Polycarboxylate, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättigter Carbonsäuren liegt im allgemeinen zwischen 5000 g/mol und 200000 g/mol, die der Copolymeren zwischen 2000 g/mol und 200000 g/mol, vorzugsweise 50000 g/mol bis 120000 g/mol, bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50000 g/mol bis The agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid , A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to
100000 g/mol auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei Carbonsäuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat enthalten. Das erste saure Monomer oder dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-Cs-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth-)acrylsäure ab. Das zweite saure Monomer oder dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure sein, wobei Maleinsäure besonders bevorzugt ist. Die dritte monomere Einheit wird in diesem Fall von Vinylalkohol und/oder vorzugsweise einem veresterten Vinylalkohol gebildet. Insbesondere sind Vinylalkohol- Derivate bevorzugt, welche einen Ester aus kurzkettigen Carbonsäuren, beispielsweise von C1-C4- Carbonsäuren, mit Vinylalkohol darstellen. Bevorzugte Terpolymere enthalten dabei 60 Gew.-% bis 95 Gew.-%, insbesondere 70 Gew.-% bis 90 Gew.-% (Meth)acrylsäure und/oder (Meth)acrylat, besonders bevorzugt Acrylsäure und/oder Acrylat, und Maleinsäure und/oder Maleinat sowie 5 Gew.- % bis 40 Gew.-%, vorzugsweise 10 Gew.-% bis 30 Gew.-% Vinylalkohol und/oder Vinylacetat.100000 g / mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. Particularly preferred are vinyl alcohol derivatives which are an ester of short chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate.
Ganz besonders bevorzugt sind dabei Terpolymere, in denen das Gewichtsverhältnis (Meth)acryl- säure und/oder (Meth)acrylat zu Maleinsäure und/oder Maleat zwischen 1 : 1 und 4:1 , vorzugsweise zwischen 2:1 und 3: 1 und insbesondere 2:1 und 2,5: 1 liegt. Dabei sind sowohl die Mengen als
auch die Gewichtsverhältnisse auf die Säuren bezogen. Das zweite saure Monomer oder dessen Salz kann auch ein Derivat einer Allylsulfonsäure sein, die in 2-Stellung mit einem Alkylrest, vorzugsweise mit einem Ci-C4-Alkylrest, oder einem aromatischen Rest, der sich vorzugsweise von Benzol oder Benzol-Derivaten ableitet, substituiert ist. Bevorzugte Terpolymere enthalten dabei 40 Gew.-% bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)acrylsäure und/oder (Meth)acry- lat, besonders bevorzugt Acrylsäure und/oder Acrylat, 10 Gew.-% bis 30 Gew.-%, vorzugsweise 15 Gew.-% bis 25 Gew.-% Methallylsulfonsäure und/oder Methallylsulfonat und als drittes Monomer 15 Gew.-% bis 40 Gew.-%, vorzugsweise 20 Gew.-% bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann dabei beispielsweise ein Mono-, Di-, Oligo- oder Polysaccharid sein, wobei Mono-, Di- oder Oligosaccharide bevorzugt sind, besonders bevorzugt ist Saccharose.Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid and / or (meth) acrylate to maleic acid and / or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1, and in particular 2: 1 and 2.5: 1. Here are both the quantities as also the weight ratios based on the acids. The second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives, is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight. % to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or methallylsulfonate and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
Durch den Einsatz des dritten Monomers werden vermutlich Sollbruchstellen in dem Polymer eingebaut, die für die gute biologische Abbaubarkeit des Polymers verantwortlich sind. Diese Terpolymere weisen im Allgemeinen eine relative Molekülmasse zwischen 1000 g/mol und 200000 g/mol, vorzugsweise zwischen 2000 g/mol und 50000 g/mol und insbesondere zwischen 3000 g/mol und 10000 g/mol auf. Sie können, insbesondere zur Herstellung flüssiger Mittel, in Form wässriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wässriger Lösungen eingesetzt werden. Alle genannten Polycarbonsäuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
Derartige organische Buildersubstanzen sind vorzugsweise in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und besonders bevorzugt von 1 Gew.-% bis 5 Gew.-% enthalten. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen, Mitteln eingesetzt. Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Alumosilikate in Waschmittelqualität, insbesondere Zeolith NaA und gegebenenfalls NaX, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 pm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 pm. Ihr Calciumbindevermögen liegt im Bereich von 100 bis 200 mg CaO pro Gramm. Geeignete Substitute oder Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die in den Mitteln als Gerüststoffe brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu S1O2 unter 0,95, insbesondere von 1 :1 ,1 bis 1 :12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na20:Si02 von 1 :2 bis 1 :2,8. Derartige amorphe Alkalisilikate sind beispielsweise unter dem Namen Portil® im Handel erhältlich.
Solche mit einem molaren Verhältnis Na20:Si02 von 1 : 1 ,9 bis 1 :2,8 werden im Rahmen der Herstellung bevorzugt als Feststoff und nicht in Form einer Lösung zugegeben. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2Six02x+i yH20 eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1 ,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese allgemeine Formel fallen, werden beispielsweise in der europäischen Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch d-Natriumdisilikate (Na2Si20s yH20) bevorzugt. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1 ,9 bis 2, 1 bedeutet, können in Mitteln, welche einen erfindungsgemäß zu verwendenden Wirkstoff enthalten, eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1 ,9 bis 3,5, werden in einer weiteren bevorzugten Ausführungsform von Waschmitteln, welche einen erfindungsgemäß verwendeten Wirkstoff enthalten, eingesetzt. Deren Gehalt an Alkalisilikaten beträgt vorzugsweise 1 Gew.- % bis 50 Gew.-% und insbesondere 5 Gew.-% bis 35 Gew.-%, bezogen auf wasserfreie Aktivsubstanz. Falls als zusätzliche Buildersubstanz auch Alkalialumosilikat, insbesondere Zeolith, vorhanden ist, beträgt der Gehalt an Alkalisilikat vorzugsweise 1 Gew.-% bis 15 Gew.-% und insbesondere 2 Gew.-% bis 8 Gew.-%, bezogen auf wasserfreie Aktivsubstanz. Das Gewichtsverhältnis Alumosilikat zu Silikat, jeweils bezogen auf wasserfreie Aktivsubstanzen, beträgt dann vorzugsweise 4:1 bis 10: 1. In Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis von amorphem Alkalisilikat zu kristallinem Alkalisilikat vorzugsweise 1 :2 bis 2: 1 und insbesondere 1 : 1 bis 2:1 . Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 μm and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding capacity is in the range of 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 0: Si0 2 of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those having a molar ratio of Na 2 O: SiO 2 of 1: 1, 9 to 1: 2.8 are preferably added as a solid and not in the form of a solution in the course of the preparation. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Six0 2x + i yH 2 0 employed in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European Patent Application EP 0 164 514. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both ß- and d-sodium disilicates (Na 2 Si 2 0s yH 2 0) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1, 9 to 2, 1, can be used in compositions which contain an active ingredient to be used according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. The content of alkali metal silicates is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2 : 1 and especially 1: 1 to 2: 1.
Zusätzlich zum genannten anorganischen Builder können weitere wasserlösliche oder wasserunlösliche anorganische Substanzen in den Mitteln, welche einen erfindungsgemäß zu verwendenden Wirkstoff enthalten, mit diesem zusammen verwendet oder in erfindungsgemäßen Verfahren eingesetzt werden, enthalten sein. Geeignet sind in diesem Zusammenhang die Alkalicarbonate, Alkalihydrogencarbonate und Alkalisulfate sowie deren Gemische. Derartiges zusätzliches anorganisches Material kann in Mengen bis zu 70 Gew.-% vorhanden sein. In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the agents containing an active ingredient to be used according to the present invention, used together with it or used in methods of the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.
Zusätzlich können die Mittel weitere in Wasch- oder Reinigungsmitteln übliche Bestandteile enthalten. Zu diesen fakultativen Bestandteilen gehören insbesondere Enzyme, Enzymstabilisatoren, Komplexbildner für Schwermetalle, beispielsweise Aminopolycarbonsäuren, Aminohydroxypolycar- bonsäuren, Polyphosphonsäuren und/oder Aminopolyphosphonsäuren, Schauminhibitoren, beispielsweise Organopolysiloxane oder Paraffine, Lösungsmittel und optische Aufheller, beispielsweise Stilbendisulfonsäurederivate. Vorzugsweise sind in Mitteln, welche einen erfindungsgemäß
verwendeten Wirkstoff enthalten, bis zu 1 Gew.-%, insbesondere 0,01 Gew.-% bis 0,5 Gew.-% optische Aufheller, insbesondere Verbindungen aus der Klasse der substituierten 4,4'-Bis-(2,4,6-tri- amino-s-triazinyl)-stilben-2,2'-disulfonsäuren, bis zu 5 Gew.-%, insbesondere 0,1 Gew.-% bis 2 Gew.-% Komplexbildner für Schwermetalle, insbesondere Aminoalkylenphosphonsäuren und deren Salze und bis zu 2 Gew.-%, insbesondere 0,1 Gew.-% bis 1 Gew.-% Schauminhibitoren enthalten, wobei sich die genannten Gewichtsanteile jeweils auf gesamtes Mittel beziehen. In addition, the agents may contain other ingredients customary in detergents or cleaners. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in agents which are in accordance with the invention used active ingredient, up to 1 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% optical brightener, in particular compounds from the class of substituted 4,4'-bis (2,4, 6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for heavy metals, especially Aminoalkylenphosphonsäuren and their Salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.
Lösungsmittel, die insbesondere bei flüssigen Mitteln eingesetzt werden können, sind neben Wasser vorzugsweise solche, die wassermischbar sind. Zu diesen gehören die niederen Alkohole, beispielsweise Ethanol, Propanol, iso-Propanol, und die isomeren Butanole, Glycerin, niedere Glykole, beispielsweise Ethylen- und Propylenglykol, und die aus den genannten Verbindungsklassen ableitbaren Ether. In derartigen flüssigen Mitteln liegen die erfindungsgemäß verwendeten Wirkstoffe in der Regel gelöst oder in suspendierter Form vor. Solvents which can be used in particular for liquid agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the active compounds used in the invention are usually dissolved or in suspended form.
Gegebenenfalls anwesende Enzyme werden vorzugsweise aus der Gruppe umfassend Protease, Amylase, Lipase, Cellulase, Hemicellulase, Oxidase, Peroxidase, Pektinase und Mischungen aus diesen ausgewählt. In erster Linie kommt aus Mikroorganismen, wie Bakterien oder Pilzen, gewonnene Protease in Frage. Sie kann in bekannter Weise durch Fermentationsprozesse aus geeigneten Mikroorganismen gewonnen werden. Proteasen sind im Handel beispielsweise unter den Namen BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® oder Maxapem® erhältlich. Die einsetzbare Lipase kann beispielsweise aus Humicola lanuginosa, aus Bacillus-Arten, aus Pseudomonas-Arten, aus Fusarium-Arten, aus Rhizopus-Arten oder aus Aspergillus-Arten gewonnen werden. Geeignete Lipasen sind beispielsweise unter den Namen Lipo- lase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase und Diosynth®-Lipase im Handel erhältlich. Geeignete Amylasen sind beispielsweise unter den Namen Maxamyl®, Termamyl®, Duramyl® und Purafect® OxAm handelsüblich. Die einsetzbare Cellulase kann ein aus Bakterien oder Pilzen gewinnbares Enzym sein, welches ein pH-Optimum vorzugsweise im schwach sauren bis schwach alkalischen Bereich von 6 bis 9,5 aufweist. Derartige Cellu- lasen sind unter den Namen Celluzyme®, Carezyme® und Ecostone® handelsüblich. Geeignete Pektinasen sind beispielsweise unter den Namen Gamanase®, Pektinex AR®, X-Pect® oder Pectaway® von Novozymes, unter dem Namen Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® von AB Enzymes und unter dem Namen Pyrolase® von Diversa Corp., San Diego, CA, USA erhältlich. Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®. Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
Zu den gegebenenfalls, insbesondere in flüssigen Mitteln vorhandenen üblichen Enzymstabilisatoren gehören Aminoalkohole, beispielsweise Mono-, Di-, Triethanol- und -propanolamin und deren Mischungen, niedere Carbonsäuren, Borsäure, Alkaliborate, Borsäure-Carbonsäure-Kombinatio-
nen, Borsäureester, Boronsäurederivate, Calciumsalze, beispielsweise Ca-Ameisensäure-Kombi- nation, Magnesiumsalze, und/oder schwefelhaltige Reduktionsmittel. The customary enzyme stabilizers present, in particular in liquid agents, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali borates, boric acid-carboxylic acid combinations. NEN, boric acid esters, boronic acid derivatives, calcium salts, for example, Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.
Zu den geeigneten Schauminhibitoren gehören langkettige Seifen, insbesondere Behenseife, Fettsäureamide, Paraffine, Wachse, Mikrokristallinwachse, Organopolysiloxane und deren Gemische, die darüber hinaus mikrofeine, gegebenenfalls silanierte oder anderweitig hydrophobierte Kieselsäure enthalten können. Zum Einsatz in partikelförmigen Mitteln sind derartige Schauminhibitoren vorzugsweise an granuläre, wasserlösliche Trägersubstanzen gebunden. Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.
Zu den bekanntlich polyesteraktiven schmutzablösevermögenden Polymeren, die zusätzlich zu den erfindungswesentlichen Wirkstoffen eingesetzt werden können, gehören Copolyester aus Dicar- bonsäuren, beispielsweise Adipinsäure, Phthalsäure oder Terephthalsäure, Diolen, beispielsweise Ethylenglykol oder Propylenglykol, und Polydiolen, beispielsweise Polyethylenglykol oder Polypropylenglykol. Zu den bevorzugt eingesetzten schmutzablösevermögenden Polyestern gehören solche Verbindungen, die formal durch Veresterung zweier Monomerteile zugänglich sind, wobei das erste Monomer eine Dicarbonsäure HOOC-Ph-COOH und das zweite Monomer ein Diol HO- (CHR11-)aOH, das auch als polymeres Diol H-(0-(CHR11-)a)bOH vorliegen kann, ist. Darin bedeutet Ph einen o-, m- oder p-Phenylenrest, der 1 bis 4 Substituenten, ausgewählt aus Alkylresten mit 1 bis 22 C-Atomen, Sulfonsäuregruppen, Carboxylgruppen und deren Mischungen, tragen kann, R11 Wasserstoff, einen Alkylrest mit 1 bis 22 C-Atomen und deren Mischungen, a eine Zahl von 2 bis 6 und b eine Zahl von 1 bis 300. Vorzugsweise liegen in den aus diesen erhältlichen Polyestern sowohl Monomerdioleinheiten -0-(CHR11-)aO- als auch Polymerdioleinheiten -(0-(CHR11-)a)bO- vor. Das molare Verhältnis von Monomerdioleinheiten zu Polymerdioleinheiten beträgt vorzugsweise 100: 1 bis 1 : 100, insbesondere 10:1 bis 1 :10. In den Polymerdioleinheiten liegt der Polymerisationsgrad b vorzugsweise im Bereich von 4 bis 200, insbesondere von 12 bis 140. Das Molekulargewicht oder das mittlere Molekulargewicht oder das Maximum der Molekulargewichtsverteilung bevorzugter schmutzablösevermögender Polyester liegt im Bereich von 250 g/mol bis 100000 g/mol, insbesondere von 500 g/mol bis 50000 g/mol. Die dem Rest Ph zugrundeliegende Säure wird vorzugsweise aus Terephthalsäure, Isophthalsäure, Phthalsäure, Trimellithsäure, Mellithsäure, den Isomeren der Sulfophthalsäure, Sulfoisophthalsäure und Sulfoterephthalsäure sowie deren Gemischen ausgewählt. Sofern deren Säuregruppen nicht Teil der Esterbindungen im Polymer sind, liegen sie vorzugsweise in Salzform, insbesondere als Alkali- oder Ammoniumsalz vor. Unter diesen sind die Natrium- und Kaliumsalze besonders bevorzugt. Gewünschtenfalls können statt des Monomers HOOC-Ph-COOH geringe Anteile, insbesondere nicht mehr als 10 Mol-% bezogen auf den Anteil an Ph mit der oben gegebenen Bedeutung, anderer Säuren, die mindestens zwei Carboxylgruppen aufweisen, im schmutzablösevermögenden Polyester enthalten sein. Zu diesen gehören beispielsweise Alkylen- und Alkenylendicarbonsäuren wie Malonsäure, Bernsteinsäure, Fumarsäure, Maleinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure und Seba- cinsäure. Zu den bevorzugten Diolen HO-(CHR11-)aOH gehören solche, in denen R11 Wasserstoff
und a eine Zahl von 2 bis 6 ist, und solche, in denen a den Wert 2 aufweist und R11 unter Wasserstoff und den Alkylresten mit 1 bis 10, insbesondere 1 bis 3 C-Atomen ausgewählt wird. Unter den letztgenannten Diolen sind solche der Formel HO-CH2-CHR11-OH, in der R11 die obengenannte Bedeutung besitzt, besonders bevorzugt. Beispiele für Diolkomponenten sind Ethylenglykol, 1 ,2- Propylenglykol, 1 ,3-Propylenglykol, 1 ,4-Butandiol, 1 ,5-Pentandiol, 1 ,6-Hexandiol, 1 ,8-Octandiol, 1 ,2-Decandiol, 1 ,2-Dodecandiol und Neopentylglykol. Besonders bevorzugt unter den polymeren Diolen ist Polyethylenglykol mit einer mittleren Molmasse im Bereich von 1000 g/mol bis 6000 g/mol. The known polyester-active soil release polymers which can be used in addition to the active compounds of the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R 11 denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -0- (CHR 11 -) a O- and also polymeric diol units ( 0- (CHR 11 -) a ) bO- before. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range of 4 to 200, particularly 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyester is in the range of 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms. Among the latter diols, those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred. Examples of diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.
Gewünschtenfalls können diese wie oben beschrieben zusammengesetzten Polyester auch endgruppenverschlossen sein, wobei als Endgruppen Alkylgruppen mit 1 bis 22 C-Atomen und Ester von Monocarbonsäuren in Frage kommen. Den über Esterbindungen gebundenen Endgruppen können Alkyl-, Alkenyl- und Arylmonocarbonsäuren mit 5 bis 32 C-Atomen, insbesondere 5 bis 18 C-Atomen, zugrundeliegen. Zu diesen gehören Valeriansäure, Capronsäure, Önanthsäure, Caprylsäure, Pelargonsäure, Caprinsäure, Undecansäure, Undecensäure, Laurinsäure, Laurolein- säure, Tridecansäure, Myristinsäure, Myristoleinsäure, Pentadecansäure, Palmitinsäure, Stearinsäure, Petroselinsäure, Petroselaidinsäure, Ölsäure, Linolsäure, Linolaidinsäure, Linolensäure, Eläostearinsäure, Arachinsäure, Gadoleinsäure, Arachidonsäure, Behensäure, Erucasäure, Brassi- dinsäure, Clupanodonsäure, Lignocerinsäure, Cerotinsäure, Melissinsäure, Benzoesäure, die 1 bis 5 Substituenten mit insgesamt bis zu 25 C-Atomen, insbesondere 1 bis 12 C-Atomen tragen kann, beispielsweise tert.-Butylbenzoesäure. Den Endgruppen können auch Hydroxymonocarbonsäuren mit 5 bis 22 C-Atomen zugrundeliegen, zu denen beispielsweise Hydroxyvaleriansäure, Hydroxy- capronsäure, Ricinolsäure, deren Hydrierungsprodukt Hydroxystearinsäure sowie o-, m- und p- Hydroxybenzoesäure gehören. Die Hydroxymonocarbonsäuren können ihrerseits über ihre Hydroxylgruppe und ihre Carboxylgruppe miteinander verbunden sein und damit mehrfach in einer Endgruppe vorliegen. Vorzugsweise liegt die Anzahl der Hydroxymonocarbonsäureeinheiten pro Endgruppe, das heißt ihr Oligomerisierungsgrad, im Bereich von 1 bis 50, insbesondere von 1 bis 10.If desired, these polyesters composed as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonsäuren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid , Arachinic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which includes hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10.
In einer bevorzugten Ausgestaltung der Erfindung werden Polymere aus Ethylenterephthalat und Polyethylenoxid-terephthalat, in denen die Polyethylenglykol-Einheiten Molgewichte von 750 g/mol bis 5000 g/mol aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxid-terephthalat 50:50 bis 90:10 beträgt, in Kombination mit einem erfindungswesentlichen Wirkstoff verwendet. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene terephthalate in which the polyethylene glycol units have molecular weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 used in combination with an active substance essential to the invention.
Die schmutzablösevermögenden Polymere sind vorzugsweise wasserlöslich, wobei unter dem Begriff„wasserlöslich“ eine Löslichkeit von mindestens 0,01 g, vorzugsweise mindestens 0,1 g des Polymers pro Liter Wasser bei Raumtemperatur und pH 8 verstanden werden soll. Bevorzugt eingesetzte Polymere weisen unter diesen Bedingungen jedoch eine Löslichkeit von mindestens 1 g pro Liter, insbesondere mindestens 10 g pro Liter auf.
Die Herstellung erfindungsgemäßer fester Mittel bietet keine Schwierigkeiten und kann auf bekannte Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Enzyme und eventuelle weitere thermisch empfindliche Inhaltsstoffe wie zum Beispiel Bleichmittel gegebenenfalls später separat zugesetzt werden. Zur Herstellung erfindungsgemäßer Mittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/l bis 950 g/l, ist ein einen Extrusionsschritt aufweisendes Verfahren bevorzugt. The soil release polymers are preferably water-soluble, the term "water-soluble" being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions. The preparation of solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the preparation of compositions according to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
Zur Herstellung von erfindungsgemäßen Mitteln in Tablettenform, die einphasig oder mehrphasig, einfarbig oder mehrfarbig und insbesondere aus einer Schicht oder aus mehreren, insbesondere aus zwei Schichten bestehen können, geht man vorzugsweise derart vor, dass man alle Bestandteile - gegebenenfalls je einer Schicht - in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßkräften im Bereich von etwa 50 bis 100 kN, vorzugsweise bei 60 bis 70 kN verpreßt. Insbesondere bei mehrschichtigen Tabletten kann es von Vorteil sein, wenn mindestens eine Schicht vorverpreßt wird. Dies wird vorzugsweise bei Preßkräften zwischen 5 und 20 kN, insbesondere bei 10 bis 15 kN durchgeführt. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Bruch- und Biegefestigkeiten von normalerweise 100 bis 200 N, bevorzugt jedoch über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 10 g bis 50 g, insbesondere von 15 g bis 40 g auf. Die Raumform der Tabletten ist beliebig und kann rund, oval oder eckig sein, wobei auch Zwischenformen möglich sind. Ecken und Kanten sind vorteilhafterweise abgerundet. Runde Tabletten weisen vorzugsweise einen Durchmesser von 30 mm bis 40 mm auf. Insbesondere die Größe von eckig oder quaderförmig gestalteten Tabletten, welche überwiegend über die Dosiervorrichtung beispielsweise der Geschirrspülmaschine eingebracht werden, ist abhängig von der Geometrie und dem Volumen dieser Dosiervorrichtung. Beispielhaft bevorzugte Ausführungsformen weisen eine Grundfläche von (20 bis 30 mm) x (34 bis 40 mm), insbesondere von 26x36 mm oder von 24x38 mm auf. For the preparation of compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
Flüssige oder pastöse erfindungsgemäße Mittel in Form von übliche Lösungsmittel, insbesondere Wasser, enthaltenden Lösungen werden in der Regel durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt. Liquid or pasty compositions according to the invention in the form of customary solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
In einer bevorzugten Ausführungsform ist ein Mittel, in das erfindungsgemäß zu verwendender Wirkstoff eingearbeitet wird, flüssig und enthält 1 Gew.-% bis 15 Gew.-%, insbesondere 2 Gew.-% bis 10 Gew.-% nichtionisches Tensid, 2 Gew.-% bis 30 Gew.-%, insbesondere 5 Gew.-% bis 20 Gew.-% synthetisches Aniontensid, bis zu 15 Gew.-%, insbesondere 2 Gew.-% bis 12,5 Gew.- % Seife, 0,5 Gew.-% bis 5 Gew.-%, insbesondere 1 Gew.-% bis 4 Gew.-% organischen Builder, insbesondere Polycarboxylat wie Citrat, bis zu 1 ,5 Gew.-%, insbesondere 0,1 Gew.-% bis 1 Gew.- % Komplexbildner für Schwermetalle, wie Phosphonat, und neben gegebenenfalls enthaltenem
Enzym, Enzymstabilisator, Färb- und/oder Duftstoff Wasser und/oder wassermischbares Lösungsmittel. In a preferred embodiment, an agent which is incorporated into the active ingredient to be used according to the invention is liquid and contains 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight, of nonionic surfactant, 2% by weight. % to 30% by weight, in particular 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular 2% by weight to 12.5% by weight of soap, 0, 5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1, 5 wt .-%, in particular 0.1 wt .-% to 1% by weight complexing agent for heavy metals, such as phosphonate, and in addition to optionally contained Enzyme, enzyme stabilizer, dye and / or fragrance water and / or water-miscible solvent.
In einer weiteren bevorzugten Ausführungsform ist ein Mittel, in das erfindungsgemäß zu verwendender Wirkstoff eingearbeitet wird, teilchenförmig und enthält bis zu 25 Gew.-%, insbesondere 5 Gew.-% bis 20 Gew.-% Bleichmittel, insbesondere Alkalipercarbonat, bis zu 15 Gew.-%, insbesondere 1 Gew.-% bis 10 Gew.-% Bleichaktivator, 20 Gew.-% bis 55 Gew.-% anorganischen Buil- der, bis zu 10 Gew.-%, insbesondere 2 Gew.-% bis 8 Gew.-% wasserlöslichen organischen Buil- der, 10 Gew.-% bis 25 Gew.-% synthetisches Aniontensid, 1 Gew.-% bis 5 Gew.-% nichtionisches Tensid und bis zu 25 Gew.-%, insbesondere 0,1 Gew.-% bis 25 Gew.-% anorganische Salze, insbesondere Alkalicarbonat und/oder -hydrogencarbonat.
In a further preferred embodiment, an agent in which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular from 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% by weight .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic Buder, up to 10 wt .-%, in particular 2 wt .-% to 8 Wt .-% of water-soluble organic Bu der, 10 wt .-% to 25 wt .-% synthetic anionic surfactant, 1 wt .-% to 5 wt .-% nonionic surfactant and up to 25 wt .-%, in particular 0.1 Wt .-% to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.
Beispiele Examples
Beispiel 1 : Monomerherstellung a) Herstellung von 3,4-Diacetoxy-2-vinyl-tetrahydrofuran Example 1: Monomer Preparation a) Preparation of 3,4-diacetoxy-2-vinyltetrahydrofuran
2,7 g 2-Vinyl-tetrahydrofuran-3,4-diol (20,7 mmol, 130,14 g/mol), erhalten nach dem Verfahren in Beispiel in EP 3 009 430 A1 , wurden mit 10 ml Acetylierungsreagenz (1 : 1 Mischung aus Essigsäureanhydrid und Pyridin) versetzt und bei Raumtemperatur über Nacht gerührt. Die gelbe Lösung wurde nacheinander mit 0,84 M HCl (2 x 10 ml), H2O (2 x 10 ml), gesättigter wässriger NaHCCb- Lösung (2 x 10 ml) und gesättigter wässriger NaCI-Lösung (1 x 10 ml) gewaschen. Die organische Phase wurde im Hochvakuum eingeengt und mit 300 ml einer Petrolether-Diethylether Mischung im Verhältnis 9:1 säulenchromatisch aufgereinigt. Man erhielt 4,3 g 3,4-Diacetoxy-2-vinyl-tetrahy- drofuran (Ausbeute 97 %) als gelbe viskose Flüssigkeit. d [13C, CDCb] = 19,69; 19,81 ;70,46; 76,25; 76,63; 79,94; 1 17,86; 130,48; 168,50; 168,81 ppm b) Herstellung von 2-(Hydroxymethyl)tetrahydrofuran-3,4-diol 2.7 g of 2-vinyl-tetrahydrofuran-3,4-diol (20.7 mmol, 130.14 g / mol), obtained by the method in Example EP 3 009 430 A1, were mixed with 10 ml of acetylating reagent (1: 1). 1 mixture of acetic anhydride and pyridine) and stirred at room temperature overnight. The yellow solution was washed successively with 0.84M HCl (2 x 10 mL), H2O (2 x 10 mL), saturated aqueous NaHCCb solution (2 x 10 mL) and saturated aqueous NaCl solution (1 x 10 mL) , The organic phase was concentrated under high vacuum and purified by column chromatography with 300 ml of a petroleum ether-diethyl ether mixture in a ratio of 9: 1. This gave 4.3 g of 3,4-diacetoxy-2-vinyl-tetrahydrofuran (yield 97%) as a yellow viscous liquid. d [ 13 C, CDCb] = 19.69; 19.81; 70.46; 76.25; 76.63; 79.94; 1 17.86; 130.48; 168.50; 168.81 ppm b) Preparation of 2- (hydroxymethyl) tetrahydrofuran-3,4-diol
Eine Mischung von 50 g Ribitol (0,329 mol) und 60 ml H2SO4 (c = 3,0 mol/l) wurde unter Rühren unter Rückfluß für 24 h erhitzt. Anschließend wurde das Reaktionsgemisch durch Zugabe von 14,4 g NaOH (0,350 mol) neutralisiert und Wasser wurde am Rationsverdampfer entfernt, bis ein dunkelbrauner Sirup erhalten wurde. Dieser wurde in ca. 150 ml Ethanol unter Rühren bei 60 °C gelöst. Salzreste wurden durch Filtration bei 60 °C über einem Faltenfilter abgetrennt. Das Filtrat wurde am Rotationsverdampfer auf 50 % des Volumens eingeengt und über Nacht bei -18 °C gelagert. Der dabei entstandene Niederschlag wurde von der flüssigen Phase abgetrennt und im Hochvakuum getrocknet. Man erhielt 40,9 g (Ausbeute 93 %) 2-(Hydroxymethyl)tetrahydrofuran-3,4-diol. d [1H, D2O] = 3,54 (dd, J = 12,3, 5, 1 Hz, 1 H); 3,73 (m, 3 H); 3,98 (m, 2 H); 4, 17 (m, 1 H) ppm d [13C, D2O] = 61 ,23; 70,97; 71 ,50; 72,14; 81 ,44 ppm c) Herstellung von 2,2-dimethyltetrahydrofuro[3,4-d][1 ,3]dioxol-4-yl)methanol A mixture of 50 g of ribitol (0.329 mol) and 60 ml of H2SO4 (c = 3.0 mol / l) was heated with stirring under reflux for 24 h. Subsequently, the reaction mixture was neutralized by adding 14.4 g of NaOH (0.350 mol) and water was removed on a ration evaporator until a dark brown syrup was obtained. This was dissolved in about 150 ml of ethanol with stirring at 60 ° C. Salt residues were separated by filtration at 60 ° C over a pleated filter. The filtrate was concentrated on a rotary evaporator to 50% of the volume and stored overnight at -18 ° C. The resulting precipitate was separated from the liquid phase and dried under high vacuum. This gave 40.9 g (yield 93%) of 2- (hydroxymethyl) tetrahydrofuran-3,4-diol. d [ 1 H, D 2 O] = 3.54 (dd, J = 12.3, 5, 1 Hz, 1 H); 3.73 (m, 3H); 3.98 (m, 2H); 4, 17 (m, 1H) ppm d [ 13 C, D2O] = 61, 23; 70.97; 71, 50; 72.14; 81, 44 ppm c) Preparation of 2,2-dimethyltetrahydrofuro [3,4-d] [1,3-dioxol-4-yl] methanol
Eine Mischung von 23,20 g (173,02 mmol) 2-(Hydroxymethyl)tetrahydrofuran-3,4-diol, 250 ml Aceton (3,40 mol) und 95 pl 98%ige wässrige H2SO4 wurde für 48 h auf 90 °C erhitzt. Dann wurden 2 Spatel NaHCCb zugesetzt und anschließend filtriert. Das neutralisierte Reaktionsgemisch wurde am Rotationsverdampfer eingeengt, bis ein hellbrauner Sirup zurückblieb. Dieser wurde bei 160 °C im Hochvakuum (2,0 x10 2 mbar) destilliert. Man erhielt 27,49 g 2,2-dimethyltetrahydrofuro[3,4- d)[1 ,3]dioxol-4-yl)methanol als farblosen Sirup; Ausbeute 92 %.
d [1H, CDC ] = 1 ,27 (s, 3H); 1 ,44 (s, 3H); 3,1 1 (s, 1 H); 3,47-3,60 (m, 2H); 3,89 (d, 2H); 4,02 (ddd, 1 H); 4,56 (dd, 1 H); 4,74 (dt, 1 H) ppm A mixture of 23.20 g (173.02 mmol) of 2- (hydroxymethyl) -tetrahydrofuran-3,4-diol, 250 ml of acetone (3.40 mol) and 95 μl of 98% aqueous H 2 SO 4 was added for 48 h heated to 90 ° C. Then 2 spatulas of NaHCCb were added and then filtered. The neutralized reaction mixture was concentrated on a rotary evaporator until a light brown syrup remained. This (2.0 x10 2 mbar) under high vacuum at 160 ° C. 27.49 g of 2,2-dimethyltetrahydrofuro [3,4-d] [1,3] dioxol-4-yl) methanol were obtained as a colorless syrup; Yield 92%. d [1 H, CDC] = 1, 27 (s, 3H); 1, 44 (s, 3H); 3.1 1 (s, 1H); 3.47-3.60 (m, 2H); 3.89 (d, 2H); 4.02 (ddd, 1H); 4.56 (dd, 1H); 4.74 (dt, 1H) ppm
d [13C, CDCb] = 24,86; 26,57; 61 ,73; 72,92; 81 ,00; 81 ,93; 84,95; 1 12,75 ppm d) Herstellung von 4-((Allyloxy)methyl)-2,2-dimethyltetrahydrofuro[3,4-d][1 ,3]dioxol d [ 13 C, CDCb] = 24.86; 26.57; 61, 73; 72.92; 81, 00; 81, 93; 84.95; 1 12.75 ppm d) Preparation of 4 - ((allyloxy) methyl) -2,2-dimethyltetrahydrofuro [3,4-d] [1,3] dioxole
Eine Lösung von 20,34 g (1 17 mmol) 2,2-Dimethyltetrahydrofuro[3,4-d][1 ,3]dioxol-4-yl)methanol in 50 ml DMF wurde portionsweise mit 2,52 g Natriumhydrid (105 mmol, 0,9 Äq.) versetzt und für 5 min gerührt, bis keine Bläschenbildung mehr auftrat. Danach wurde das Reaktionsgemisch auf 0 °C gekühlt und tropfenweise mit 13,1 ml Allylbromid (152 mmol, 1 ,3 Äq.) versetzt und 48 h bei Raumtemperatur gerührt. Das Reaktionsgemisch wurde mit 30 ml vollentsaltzem Wasser und 2 mal je 30 ml Diethylether extrahiert. Die vereinigten organischen Phasen wurden mit jeweils 20 ml gesättigter wässriger NaHCCb-Lösung und gesättigter wässriger NaCI-Lösung gewaschen und am Rotationsverdampfer bis zu einem gelben Sirup eingeengt. Dieser wurde im Hochvakuum destilliert (95 °C, 2,9 x 10 2 mbar). Man erhielt 19,38 g 4-((Allyloxy)methyl)-2,2-dimethyltetrahydrofuro[3,4- d][1 ,3]dioxol als farblose Flüssigkeit, Ausbeute 77,5 %. d [1H, CDCb] = 1 ,26 (s, 3H); 1 ,43 (s, 3H); 3,44 (dd, 2H); 3,82-3,98 (m, 4H); 4,04-4,12 (m, 1 H); 4,64 (dd, 1 H); 4,73 (ddd, 1 H); 5, 10 (dt, 1 H); 5,17 (dt, 1 H); 5,72-5,87 (m, 1 H) ppm A solution of 20.34 g (1 17 mmol) of 2,2-dimethyltetrahydrofuro [3,4-d] [1,3-dioxol-4-yl] methanol in 50 ml of DMF was added portionwise with 2.52 g of sodium hydride (105 mmol, 0.9 eq.) and stirred for 5 min until no more bubbling occurred. Thereafter, the reaction mixture was cooled to 0 ° C and treated dropwise with 13.1 ml of allyl bromide (152 mmol, 1, 3 eq.) And stirred for 48 h at room temperature. The reaction mixture was extracted with 30 ml of deionized water and twice with 30 ml of diethyl ether each time. The combined organic phases were washed with 20 ml of saturated aqueous NaHCCb solution and saturated aqueous NaCl solution and concentrated on a rotary evaporator to a yellow syrup. This was distilled under high vacuum (95 ° C, 2.9 x 10 2 mbar). This gave 19.38 g of 4 - ((allyloxy) methyl) -2,2-dimethyltetrahydrofuro [3,4-d] [1,3] dioxole as a colorless liquid, yield 77.5%. d [ 1 H, CDCb] = 1, 26 (s, 3H); 1, 43 (s, 3H); 3.44 (dd, 2H); 3.82-3.98 (m, 4H); 4.04-4.12 (m, 1H); 4.64 (dd, 1H); 4.73 (ddd, 1H); 5, 10 (dt, 1H); 5.17 (dt, 1H); 5.72-5.87 (m, 1H) ppm
d f3C, CDCb] = 24,90; 26,57; 70,92; 72,27; 74,02; 81 ,39; 82,66; 83,46; 1 12,33; 1 16,84; 134,36 ppm df 3 C, CDCb] = 24.90; 26.57; 70.92; 72.27; 74.02; 81, 39; 82.66; 83.46; 1 12.33; 1 16.84; 134.36 ppm
Beispiel 2: Polymerherstellung a) Copolymerisation von 3,4-Diacetoxy-2-vinyl-tetrahydrofuran mit Methylmaleimid Example 2 Polymer Preparation a) Copolymerization of 3,4-diacetoxy-2-vinyltetrahydrofuran with methylmaleimide
Eine Lösung von 319 mg 3,4-Diacetoxy-2-vinyl-tetrahydrofuran (1 ,5 mmol), erhalten in Beispiel 1a), 158 mg Methylmaleimid (1 ,4 mmol) und 15,7 mg Azobis-isobutyronitril (AIBN, 0,10 mmol) in 2 ml Toluol wurden unter Durchleiten von Stickstoff entgast und anschließend im verschlossenen Kolben unter N2 für ca. 24 Stunden auf 80°C erhitzt. Danach wurde das Lösemittel entfernt und 44,4 mg AIBN (0,27 mmol) in 3 ml Dimethylformamid (DMF) wurden zugegeben. Der Reaktionsansatz wurde für weitere 42 Stunden auf 80°C erhitzt. Danach wurde das entstandene Polymer durch Eintropfen in 20 ml Diethylether ausgefällt und durch GPC in DMF mit 0,1 % LiBr charakterisiert. Zur Molmassenkalibrierung wurden Polystyrolstandards verwendet. A solution of 319 mg of 3,4-diacetoxy-2-vinyl-tetrahydrofuran (1.5 mmol), obtained in Example 1a), 158 mg of methylmaleimide (1.4 mmol) and 15.7 mg of azobis-isobutyronitrile (AIBN, 0 , 10 mmol) in 2 ml of toluene were degassed while passing nitrogen through and then heated in a sealed flask under N2 for about 24 hours at 80 ° C. Thereafter, the solvent was removed and 44.4 mg of AIBN (0.27 mmol) in 3 ml of dimethylformamide (DMF) was added. The reaction was heated at 80 ° C for an additional 42 hours. Thereafter, the resulting polymer was precipitated by dropping in 20 ml of diethyl ether and characterized by GPC in DMF with 0.1% LiBr. For molecular weight calibration polystyrene standards were used.
Mn = 8500 g-mol 1 , Mw = 13400 g mol-1. b) Copolymerisat aus 2-Vinyl-tetrahydrofuran-3,4-diol mit Methylmaleimid
Eine Lösung von 307 mg 2-Vinyl-tetrahydrofuran-3,4-diol (2,3 mmol) (hergestellt wie im Beispiel der EP 3 009 430 beschrieben), 257 mg Methylmaleimid (2,3 mmol) und 19,3 mg Azobis-isobutyro- nitril (AIBN, 0, 12 mmol) in 2 ml Toluol und 2 ml Ethanol wurde unter Durchleiten von Stickstoff entgast und anschließend im verschlossenen Kolben unter N2 für ca. 24 Stunden auf 80°C erhitzt. Danach wurde das Lösemittel entfernt und 52,2 mg AIBN (0,32 mmol) in 3 ml Dimethylformamid (DMF) wurden zugegeben. Der Reaktionsansatz wurde für weitere 42 Stunden auf 80°C erhitzt. Danach wurde das entstandene Polymer durch Eintropfen in 20 ml Diethylether ausgefällt und durch GPC in DMF mit 0, 1 % LiBr charakterisiert. Zur Molmassenkalibrierung wurden Polystyrolstandards verwendet. Mn = 8500 g-mol 1 , Mw = 13400 g mol -1 . b) Copolymer of 2-vinyl-tetrahydrofuran-3,4-diol with methylmaleimide A solution of 307 mg of 2-vinyl-tetrahydrofuran-3,4-diol (2.3 mmol) (prepared as described in the example of EP 3 009 430), 257 mg of methylmaleimide (2.3 mmol) and 19.3 mg of azobis -isobutyronitrile (AIBN, 0.12 mmol) in 2 ml of toluene and 2 ml of ethanol was degassed while passing nitrogen through it and then heated in a sealed flask under N2 for about 24 hours at 80 ° C. Thereafter, the solvent was removed and 52.2 mg of AIBN (0.32 mmol) in 3 ml of dimethylformamide (DMF) was added. The reaction was heated at 80 ° C for an additional 42 hours. Thereafter, the resulting polymer was precipitated by dropping in 20 ml of diethyl ether and characterized by GPC in DMF with 0.1% LiBr. For molecular weight calibration polystyrene standards were used.
Mn = 4000 g mol 1 , Mw = 7500 g mol-1. c) Copolymerisat aus 2-Vinyl-tetrahydrofuran-3,4-diol und Maleinsäure (C) Mn = 4000 g mol 1 , Mw = 7500 g mol -1 . c) Copolymer of 2-vinyl-tetrahydrofuran-3,4-diol and maleic acid (C)
Eine Mischung aus 0,5 g 3,4-Diacetoxy-2-vinyl-tetrahydrofuran (2,33 mmol) aus Besispiel 1 a),A mixture of 0.5 g of 3,4-diacetoxy-2-vinyl-tetrahydrofuran (2.33 mmol) from Example 1 a),
0,46 g Maleinsäureanhydrid (4,66 mmol) und 47 mg Azobis-isobutyronitril (AIBN, 0,28 mmol) wurde unter Durchleiten von Stickstoff entgast und anschließend im verschlossenen Kolben unter N2 für ca. 20 Stunden auf 90°C erhitzt. Das Produkt wurde in wenigen ml Dichlormethan gelöst und in 200 ml Petrolether ausgefällt. Das beige Pulver wurde abfiltriert und im Vakuumtrockenschrank getrocknet. 0.46 g of maleic anhydride (4.66 mmol) and 47 mg of azobisisobutyronitrile (AIBN, 0.28 mmol) was degassed while passing nitrogen through it and then heated in a sealed flask under N2 for about 20 hours at 90 ° C. The product was dissolved in a few ml of dichloromethane and precipitated in 200 ml of petroleum ether. The beige powder was filtered off and dried in a vacuum oven.
Das Produkt wurde in 5 ml Ethanol gelöst und nach Zugabe von 10 ml 10%iger wässriger Natronlauge für 30 Minuten bei 50°C gerührt und zum Copolymer C hydrolisiert. d) Copolymerisat aus 2-Allyloxymethyl-tetrahydrofuran-3,4-diol mit Maleinsäure (A) The product was dissolved in 5 ml of ethanol and stirred after addition of 10 ml of 10% aqueous sodium hydroxide solution for 30 minutes at 50 ° C and hydrolyzed to the copolymer C. d) Copolymer of 2-allyloxymethyl-tetrahydrofuran-3,4-diol with maleic acid (A)
Eine Lösung von 2 g 4-((Allyloxy)methyl)-2,2-dimethyltetrahydrofuro[3,4-d][1 ,3]dioxol (9,32 mmol), hergestellt in Beispiel 1d), 1 ,83 g Maleinsäureanhydrid (18,64 mmol) und 190 mg Azobis-isobutyronitril (AIBN, 1 , 12 mmol) in 2 ml Toluol wurde unter Durchleiten von Stickstoff entgast und im verschlossenen Kolben unter N2 für ca. 20 Stunden auf 90°C erhitzt. Danach wurde das Lösemittel entfernt und der so erhaltene gelbe Rückstand wurde in 40 ml Essigsäure/Wasser (4: 1 ) gelöst, anschließend auf 80°C erwärmt und für 21 Stunden gerührt. Essigsäure und Wasser wurde im Vakuum entfernt und der erhaltene Feststoff in 70 ml Wasser gelöst und dialysiert. Das gefällte Copolymer A wurde durch GPC in Wasser charakterisiert. Zur Molmassenkalibrierung wurden Polyacrylsäurestandards verwendet. A solution of 2 g of 4 - ((allyloxy) methyl) -2,2-dimethyltetrahydrofuro [3,4-d] [1,3] dioxole (9.32 mmol) prepared in Example 1d), 1.83 g of maleic anhydride (18.64 mmol) and 190 mg of azobis-isobutyronitrile (AIBN, 1, 12 mmol) in 2 ml of toluene was degassed while passing nitrogen and heated in the sealed flask under N2 for about 20 hours at 90 ° C. Thereafter, the solvent was removed and the resulting yellow residue was dissolved in 40 ml of acetic acid / water (4: 1), then heated to 80 ° C and stirred for 21 hours. Acetic acid and water were removed in vacuo and the resulting solid dissolved in 70 ml of water and dialyzed. The precipitated copolymer A was characterized by GPC in water. For molecular weight calibration, polyacrylic acid standards were used.
Mn = 2700 g mol-1 , Mw = 15500 g-mol 1 e) Copolymerisat aus 2-Allyloxymethyl-tetrahydrofuran-3,4-diol mit Maleimid (B)
Eine Lösung von 2 g 2-Allyloxymethyl-tetrahydrofuran-3,4-diol (9,32 mmol), 1 ,81 g Maleimid (18,64 mmol) und 190 mg Azobis-isobutyronitril (AIBN, 1 , 12 mmol) in 2 ml Dimethylsulfoxid wurde unter Durchleiten von Stickstoff entgast und anschließend im verschlossenen Kolben unter N2 für ca. 120 Stunden auf 90°C erhitzt. Danach wurde das entstandene Polymer durch Eintropfen in 20 m Toluol ausgefällt, in 40 ml Essigsäure/Wasser (4:1 ) gelöst, anschließend auf 80°C erwärmt und für 27 Stunden gerührt. Der Niederschlag aus Copolymer B wurde abfiltriert, getrocknet und durch GPC in Wasser charakterisiert. Mn = 2700 g mol -1 , Mw = 15500 g-mol 1 e) Copolymer of 2-allyloxymethyl-tetrahydrofuran-3,4-diol with maleimide (B) A solution of 2 g of 2-allyloxymethyl-tetrahydrofuran-3,4-diol (9.32 mmol), 1.81 g of maleimide (18.64 mmol) and 190 mg of azobis-isobutyronitrile (AIBN, 1.2 mmol) in 2 ml of dimethyl sulfoxide was degassed while passing nitrogen through it and then heated in the sealed flask under N 2 for about 120 hours at 90 ° C. Thereafter, the resulting polymer was precipitated by dropping in 20 m of toluene, dissolved in 40 ml of acetic acid / water (4: 1), then heated to 80 ° C and stirred for 27 hours. The precipitate of copolymer B was filtered off, dried and characterized by GPC in water.
Beispiel 3: Waschversuche Example 3: Washing Tests
Mit den in den nachfolgenden Tabelle angegebenen standardisierten Anschmutzungen versehene Testtextilien wurden bei 40 °C mit einem handelsüblichen bleichmittelfreien Flüssigwaschmittel, dem man 5 Gew.-% bezogen auf das Waschmittel an jeweils einen der in Beispiel 2 hergestellten Polymere oder zum Vergleich die gleichen Mengen der handelsüblichen Polymere Polyethylenimin (Sokalan® HP 20; V1 ) oder Polyacrylat (Acusol® 445N; V2) zugesetzt hatte, bei einer Dosierung des Waschmittels von jeweils 4, 1 g/l in Leitungswasser von 16 °dH, gewaschen. Nach Auswaschen mit Wasser und Trocknung wurde der Weißgrad der Testtextilien spektralphotometrisch (Minolta® CR400-1 ) bestimmt. In den nachfolgenden Tabellen sind die Differenzen der Remissionswerte (jeweils in %) zum gleichen Einsatz des ansonsten gleich zusammengesetzten Waschmittels ohne das Polymer als Mittelwerte aus 3 Bestimmungen angegeben. Test textiles provided with the standardized stains given in the table below were at 40 ° C. with a commercial bleach-free liquid detergent containing 5% by weight, based on the detergent, of one of the polymers prepared in Example 2 or, for comparison, the same amounts of the commercial one Polymer polyethylenimine (Sokalan® HP 20; V1) or polyacrylate (Acusol® 445N; V2) had been added, with a dosage of the detergent of 4, 1 g / l in tap water of 16 ° dH, washed. After washing with water and drying, the whiteness of the test textiles was determined spectrophotometrically (Minolta® CR400-1). In the following tables, the differences of the remission values (in each case in%) for the same use of the otherwise identically composed detergent without the polymer are given as mean values from 3 determinations.
Tabelle 1 : Waschergebnisse (Remissionsdifferenz zum polymerfreien Mittel) mit Copolymer A im Vergleich mit Acusol® 445N; V2
Table 1: Wash results (remission difference to polymer-free agent) with Copolymer A compared with Acusol® 445N; V2
Tabelle 2: Waschergebnisse (Remissionsdifferenz zum polymerfreien Mittel) mit Copolymer B im Vergleich mit Sokalan® HP 20; V1
Table 2: Wash results (remission difference to the polymer-free agent) with Copolymer B in comparison with Sokalan® HP 20; V1
Tabelle 3: Waschergebnisse (Remissionsdifferenz zum polymerfreien Mittel) mit Copolymer C im Vergleich mit Sokalan® HP 20; V1 , und mit Acusol® 445N; V2
Die Waschmittel mit den erfindungsgemäß zu verwendenden Wirkstoffen zeigten eine deutlich bessere Primärwaschleistung als ein ansonsten gleich zusammengesetztes Mittel, dem diese fehlten, oder ein Mittel, das ein Homopolymer des Standes der Technik enthielt.
Table 3: Wash results (remission difference to the polymer-free agent) with copolymer C in comparison with Sokalan® HP 20; V1, and with Acusol® 445N; V2 The detergents containing the active ingredients to be used according to the invention showed a significantly better primary washing performance than an otherwise equally composed composition which they lacked or an agent which contained a homopolymer of the prior art.
Claims
1. Copolymer, erhältlich durch radikalische Copolymerisation von Verbindungen der allgemeinen Formel I, 1. copolymer obtainable by free-radical copolymerization of compounds of general formula I,
in der R1 für -CR2=CR3R4 oder -CH2-0-CH2-CR2=CR3R4 und R2, R3 und R4 unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen stehen, mit a,ß-monoethylenisch ungesättigten Carbonsäuren, Carbonsäureestern, Carbonsäureanhydriden, Carbonsäureamiden, Carbonsäureimiden, Nitrilen und deren Mischungen. in the R 1 for -CR 2 = CR 3 R 4 or -CH 2 -O-CH 2 -CR 2 = CR 3 R 4 and R 2 , R 3 and R 4 are independently H or an alkyl group having 1 to 3 C atoms, with a, ß-monoethylenically unsaturated carboxylic acids, carboxylic acid esters, carboxylic anhydrides, carboxylic acid amides, Carbonsäureimiden, nitriles and mixtures thereof.
2. Verwendung von Copolymeren, erhältlich durch radikalische Copolymerisation von Verbindungen der allgemeinen Formel I, 2. Use of copolymers obtainable by free-radical copolymerization of compounds of the general formula I,
in der R1 für -CR2=CR3R4 oder -CH2-0-CH2-CR2=CR3R4 und R2, R3 und R4 unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen stehen, mit a,ß-monoethylenisch ungesättigten Carbonsäuren, Carbonsäureestern, Carbonsäureanhydriden, Carbonsäureamiden, Carbonsäureimiden, Nitrilen und deren Mischungen, zur Verstärkung der Primärwaschkraft von Wasch- oder Reinigungsmitteln beim Waschen von Textilien oder beim Reinigen harter Oberflächen gegenüber Anschmutzungen. in the R 1 for -CR 2 = CR 3 R 4 or -CH 2 -O-CH 2 -CR 2 = CR 3 R 4 and R 2 , R 3 and R 4 are independently H or an alkyl group having 1 to 3 C atoms, with a, ß-monoethylenically unsaturated carboxylic acids, carboxylic acid esters, carboxylic anhydrides, carboxylic acid amides, Carbonsäureimiden, nitriles and mixtures thereof, to enhance the Primärwaschkraft of detergents or cleaning agents when washing textiles or when cleaning hard surfaces against stains.
3. Verwendung nach Anspruch 2, dadurch gekennzeichnet, dass man das Copolymer einer wasch- oder reinigungsmittelhaltigen wässrigen Flotte zusetzt oder es als Bestandteil eines Wasch- oder Reinigungsmittels in die Flotte einbringt, wobei die Konzentration an Copolymer in der Flotte im Bereich von 0,004 g/l bis 0,5 g/l, insbesondere von 0,01 g/l bis 0,1 g/l liegt. 3. Use according to claim 2, characterized in that the copolymer is added to a washing or cleaning agent-containing aqueous liquor or incorporates it as a constituent of a washing or cleaning agent in the liquor, wherein the concentration of copolymer in the liquor in the range of 0.004 g / l to 0.5 g / l, in particular from 0.01 g / l to 0.1 g / l.
4. Verfahren zum Entfernen von Anschmutzungen von Textilien oder harten Oberflächen durch Kontaktieren des reinigungsbedürftigen Textils oder der reinigungsbedürftigen harten Oberfläche mit einer wässrigen Flotte, in der sich ein Wasch- oder Reinigungsmittel und ein Co-
polymer, erhältlich durch radikalische Copolymerisation von Verbindungen der allgemeinen Formel I, 4. A method of removing stains from textiles or hard surfaces by contacting the textile or surface requiring cleaning with an aqueous liquor containing a detergent or coagulant and a coagulant. polymer, obtainable by free-radical copolymerization of compounds of general formula I,
in der R1 für -CR2=CR3R4 oder -CH2-0-CH2-CR2=CR3R4 und R2, R3 und R4 unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen stehen, mit a,ß-monoethylenisch ungesättigten Carbonsäuren, Carbonsäureestern, Carbonsäureanhydriden, Carbonsäureamiden, Carbonsäureimiden, Nitrilen und deren Mischungen, befindet. in the R 1 for -CR 2 = CR 3 R 4 or -CH 2 -O-CH 2 -CR 2 = CR 3 R 4 and R 2 , R 3 and R 4 are independently H or an alkyl group having 1 to 3 C atoms are, with a, ß-monoethylenically unsaturated carboxylic acids, carboxylic acid esters, carboxylic anhydrides, carboxylic acid amides, Carbonsäureimiden, nitriles and mixtures thereof, is located.
5. Verwendung nach Anspruch 2 oder 3 oder Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass es sich bei den Anschmutzungen um enzymatisch oder oxidativ enttfernbare Ansschmutzungen handelt. 5. Use according to claim 2 or 3 or method according to claim 4, characterized in that it is enzymatically or oxidatively resettable pollutants in the soiling.
6. Wasch- oder Reinigungsmittel, enthaltend ein Copolymer, erhältlich durch radikalische Copolymerisation von Verbindungen der allgemeinen Formel I, 6. washing or cleaning compositions containing a copolymer obtainable by free-radical copolymerization of compounds of general formula I,
in der R1 für -CR2=CR3R4 oder -CH2-0-CH2-CR2=CR3R4 und R2, R3 und R4 unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen stehen, mit a,ß-monoethylenisch ungesättigten Carbonsäuren, Carbonsäureestern, Carbonsäureanhydriden, Carbonsäureamiden, Carbonsäureimiden, Nitrilen und deren Mischungen. in the R 1 for -CR 2 = CR 3 R 4 or -CH 2 -O-CH 2 -CR 2 = CR 3 R 4 and R 2 , R 3 and R 4 are independently H or an alkyl group having 1 to 3 C atoms, with a, ß-monoethylenically unsaturated carboxylic acids, carboxylic acid esters, carboxylic anhydrides, carboxylic acid amides, Carbonsäureimiden, nitriles and mixtures thereof.
7. Mittel nach Anspruch 6, dadurch gekennzeichnet, dass es 0,1 Gew.-% bis 10 Gew.-%, insbesondere 0,3 Gew.-% bis 2 Gew.-% des Copolymers enthält. 7. Composition according to claim 6, characterized in that it contains 0.1 wt .-% to 10 wt .-%, in particular 0.3 wt .-% to 2 wt .-% of the copolymer.
8. Copolymer, Verwendung, Verfahren oder Mittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass in dem Copolymer die aus der Verbindung der allgemeinen Formel I stammenden Einheiten und die aus der a,b-monoethylenisch ungesättigten Carbonsäure und/oder deren Derivaten stammenden Einheiten vorzugsweise in Molverhältnissen im Bereich von 1 :1 bis 1 :9, insbesondere von 1 : 1 ,5 bis 1 :5 vorliegen.
8. A copolymer, use, method or composition according to any one of the preceding claims, characterized in that in the copolymer originating from the compound of the general formula I units and derived from the a, b-monoethylenically unsaturated carboxylic acid and / or derivatives thereof units preferably in molar ratios in the range from 1: 1 to 1: 9, in particular from 1: 1, 5 to 1: 5.
9. Copolymer, Verwendung, Verfahren oder Mittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Copolymer ein mittleres Molekulargewicht in Bereich von 500 g/mol bis 50000 g/mol, insbesondere von 2000 g/mol bis 10000 g/mol aufweist. 9. Copolymer, use, method or composition according to one of the preceding claims, characterized in that the copolymer has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 2000 g / mol to 10,000 g / mol.
10. Copolymer, Verwendung, Verfahren oder Mittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die a,b-monoethylenisch ungesättigten Carbonsäuren und deren Derivate aus Säuren wie Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Estern wie beispielsweise Dimethylmaleat, Dieethylmaleat, Dimethylfumarat, Dieethylfumarat, Methylacrylat, Ethylacrylat, n-Propylacrylat, Isopropylacrylat, Butylacrylat, Pentylacrylat, He- xylacrylat, 2-Ethylhexylacrylat, Nonylacrylat, Laurylacrylat, Trimethylcyclohexylacrylat, t- Butylcyclohexylacrylat, Benzylacrylat, Hydroxyethylacrylat, Ethoxyethylacrylat, 10. A copolymer, use, method or composition according to any one of the preceding claims, characterized in that the a, b-monoethylenically unsaturated carboxylic acids and their derivatives of acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, esters such as dimethyl maleate, diethyl maleate, dimethyl fumarate, Dimethyl fumarate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, trimethylcyclohexyl acrylate, t-butylcyclohexyl acrylate, benzyl acrylate, hydroxyethyl acrylate, ethoxyethyl acrylate,
Ethoxyethoxyethylacrylat, Aminoethylacrylat, t-Butylaminoethylacrylat, N,N-Dimethylamino- ethylacrylat, N,N-Diethylaminoethylacrylat, und entsprechende Methacrylate, Amiden wie Maleinsäurediamid, Fumarsäurediamid, Acrylamid, N-Methylacrylamid, N-Ethylacrylamid, N- n-Propylacrylamid, N-Isopropylacrylamid, N-Butylacrylamid, N-Octylacrylamid, N-Dodecyl- acrylamid, N-Octadecylacrylamid, N-Butoxymethylacrylamid, N,N-Dimethylacrylamid, N,N- Diethylacrylamid, N,N-Dipropylacrylamid, N,N-Dibutylacrylamid, N-(N‘,N‘-Dimethylami- no)ethylacrylamid, N-(N‘,N‘-Diethylamino)ethylacrylamid, Methacrylamid und entsprechend N-substituierte Methacrylamide, Anhydriden wie Maleinsäureanhydrid, Imiden wie N-Acroyl- und N-Methacroylbutyro, -capro- und -valerolactam, Maleinimid, N-Phenyl- und N-Methyl- Maleinimid, Nitrilen wie beispielsweise Acetonitril und Fumarodinitril, die einzeln oder als Mischungen von zwei oder mehreren dieser Verbindungen vorliegen können, ausgewählt werden, und/oder dass in der Verbindung der Formel I R2, R3 und R4 gleich sind und/oder in der Verbindung der Formel I mindestens einer der Reste R2, R3 und R4 Wasserstoff ist, und/oder dass die aus dem a,b-monoethylenisch ungesättigten Monomer stammenden Carbonsäuregruppen, Carbonsäureestergruppen, Carbonsäureanhydridgruppen, Carbonsäureamidgruppen oder Carbonsäureimidgruppen, ganz oder zumindest anteilig, hydrolysiert in Salzform vorliegen. Ethoxyethoxyethyl acrylate, aminoethyl acrylate, t-butylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, and corresponding methacrylates, amides such as maleic acid diamide, fumaric acid diamide, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-n-propylacrylamide, N- Isopropylacrylamide, N-butylacrylamide, N-octylacrylamide, N-dodecylacrylamide, N-octadecylacrylamide, N-butoxymethylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dipropylacrylamide, N, N-dibutylacrylamide, N- (N ', N'-dimethylamino) ethylacrylamide, N- (N', N'-diethylamino) ethylacrylamide, methacrylamide and correspondingly N-substituted methacrylamides, anhydrides such as maleic anhydride, imides such as N-acroyl- and N-methacroylbutyro, capro and valerolactam, maleimide, N-phenyl and N-methyl maleimide, nitriles such as acetonitrile and fumarodinitrile, which may be present individually or as mixtures of two or more of these compounds, and / or that in Ve b of the formula IR 2 , R 3 and R 4 are the same and / or in the compound of formula I at least one of R 2 , R 3 and R 4 is hydrogen, and / or that of the a, b-monoethylenically unsaturated Monomer-derived carboxylic acid groups, carboxylic acid ester groups, carboxylic anhydride groups, carboxamide or Carbonsäureimidgruppen, all or at least proportionately hydrolyzed in salt form.
1 1. Verbindungen der allgemeinen Formel la, 1 1. Compounds of the general formula Ia,
in der R1 für -CH2-0-CH2-CR2=CR3R4 und R2, R3 und R4 unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen stehen, sowie deren Derivate, bei denen die beiden Hydroxylgruppen durch Aufziehen üblicher Schutzgruppen, insbesondere als Acetal wie
Tetrahydropyranylether, als Ketal wie Acetonid oder als Carbonsäureester wie Acetat, geschützt sind.
in which R 1 is -CH 2 -O-CH 2 -CR 2 = CR 3 R 4 and R 2 , R 3 and R 4 independently of one another are H or an alkyl group having 1 to 3 C atoms, and derivatives thereof, in which the two hydroxyl groups by raising conventional protecting groups, in particular as acetal such Tetrahydropyranylether, as ketal such as acetonide or as a carboxylic acid ester such as acetate, are protected.
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DE102017010656.8A DE102017010656A1 (en) | 2017-11-17 | 2017-11-17 | Detergents and cleaning agents with polymeric agent |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021078554A1 (en) * | 2019-10-21 | 2021-04-29 | Henkel Ag & Co. Kgaa | Anti-redeposition detergents |
WO2023064749A1 (en) | 2021-10-14 | 2023-04-20 | The Procter & Gamble Company | A fabric and home care product comprising cationic soil release polymer and lipase enzyme |
EP4321604A1 (en) | 2022-08-08 | 2024-02-14 | The Procter & Gamble Company | A fabric and home care composition comprising surfactant and a polyester |
WO2024094803A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2024094800A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2024094802A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2024119298A1 (en) | 2022-12-05 | 2024-06-13 | The Procter & Gamble Company | Fabric and home care composition comprising a polyalkylenecarbonate compound |
EP4386074A1 (en) | 2022-12-16 | 2024-06-19 | The Procter & Gamble Company | Fabric and home care composition |
WO2024129520A1 (en) | 2022-12-12 | 2024-06-20 | The Procter & Gamble Company | Fabric and home care composition |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102019007303A1 (en) * | 2019-10-21 | 2021-04-22 | Henkel Ag & Co. Kgaa | Graying-inhibiting detergents |
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EP0164514A1 (en) | 1984-04-11 | 1985-12-18 | Hoechst Aktiengesellschaft | Use of lamellar crystalline sodium silicates in water-softening processes |
WO2001057171A1 (en) | 2000-02-02 | 2001-08-09 | Unilever Plc | Polymers for laundry applications |
EP3009430A1 (en) | 2014-10-17 | 2016-04-20 | Jürgen Klankermayer | Vinyltetrahydrofuranes |
WO2016162254A1 (en) * | 2015-04-10 | 2016-10-13 | Henkel Ag & Co. Kgaa | Detergents and cleaning products containing a polymer active ingredient |
WO2016162253A1 (en) * | 2015-04-10 | 2016-10-13 | Henkel Ag & Co. Kgaa | Detergents and cleaning products containing a polymer active ingredient |
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2017
- 2017-11-17 DE DE102017010656.8A patent/DE102017010656A1/en not_active Withdrawn
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2018
- 2018-11-02 EP EP18796644.5A patent/EP3710504A1/en not_active Withdrawn
- 2018-11-02 WO PCT/EP2018/079971 patent/WO2019096590A1/en unknown
Patent Citations (5)
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EP0164514A1 (en) | 1984-04-11 | 1985-12-18 | Hoechst Aktiengesellschaft | Use of lamellar crystalline sodium silicates in water-softening processes |
WO2001057171A1 (en) | 2000-02-02 | 2001-08-09 | Unilever Plc | Polymers for laundry applications |
EP3009430A1 (en) | 2014-10-17 | 2016-04-20 | Jürgen Klankermayer | Vinyltetrahydrofuranes |
WO2016162254A1 (en) * | 2015-04-10 | 2016-10-13 | Henkel Ag & Co. Kgaa | Detergents and cleaning products containing a polymer active ingredient |
WO2016162253A1 (en) * | 2015-04-10 | 2016-10-13 | Henkel Ag & Co. Kgaa | Detergents and cleaning products containing a polymer active ingredient |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2021078554A1 (en) * | 2019-10-21 | 2021-04-29 | Henkel Ag & Co. Kgaa | Anti-redeposition detergents |
WO2023064749A1 (en) | 2021-10-14 | 2023-04-20 | The Procter & Gamble Company | A fabric and home care product comprising cationic soil release polymer and lipase enzyme |
EP4321604A1 (en) | 2022-08-08 | 2024-02-14 | The Procter & Gamble Company | A fabric and home care composition comprising surfactant and a polyester |
WO2024036126A1 (en) | 2022-08-08 | 2024-02-15 | The Procter & Gamble Company | A fabric and home care composition comprising surfactant and a polyester |
WO2024094803A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2024094800A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2024094802A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2024119298A1 (en) | 2022-12-05 | 2024-06-13 | The Procter & Gamble Company | Fabric and home care composition comprising a polyalkylenecarbonate compound |
WO2024129520A1 (en) | 2022-12-12 | 2024-06-20 | The Procter & Gamble Company | Fabric and home care composition |
EP4386074A1 (en) | 2022-12-16 | 2024-06-19 | The Procter & Gamble Company | Fabric and home care composition |
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DE102017010656A1 (en) | 2019-05-23 |
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