EP3114198B1 - Pre-portioned cleaning agent comprising at least two separate liquid preparations - Google Patents
Pre-portioned cleaning agent comprising at least two separate liquid preparations Download PDFInfo
- Publication number
- EP3114198B1 EP3114198B1 EP15708188.6A EP15708188A EP3114198B1 EP 3114198 B1 EP3114198 B1 EP 3114198B1 EP 15708188 A EP15708188 A EP 15708188A EP 3114198 B1 EP3114198 B1 EP 3114198B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid preparation
- cleaning agent
- acid
- agent according
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 238000002360 preparation method Methods 0.000 title claims description 120
- 239000007788 liquid Substances 0.000 title claims description 108
- 239000012459 cleaning agent Substances 0.000 title claims description 45
- -1 - CH2CH(CH3)2 Chemical group 0.000 claims description 62
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 58
- 239000003599 detergent Substances 0.000 claims description 58
- 239000002736 nonionic surfactant Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 41
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 30
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 30
- 238000004851 dishwashing Methods 0.000 claims description 28
- 102000004190 Enzymes Human genes 0.000 claims description 27
- 108090000790 Enzymes Proteins 0.000 claims description 27
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 24
- 238000009463 water soluble packaging Methods 0.000 claims description 23
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 10
- 235000013772 propylene glycol Nutrition 0.000 claims description 10
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000007844 bleaching agent Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- 239000002280 amphoteric surfactant Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000000845 anti-microbial effect Effects 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000003352 sequestering agent Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 101100345345 Arabidopsis thaliana MGD1 gene Proteins 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims 1
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 claims 1
- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 33
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- 229940088598 enzyme Drugs 0.000 description 22
- 239000002253 acid Substances 0.000 description 20
- 239000011734 sodium Substances 0.000 description 20
- 229920002125 SokalanĀ® Polymers 0.000 description 19
- 229910019142 PO4 Inorganic materials 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 18
- 235000021317 phosphate Nutrition 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 16
- 150000007513 acids Chemical class 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 235000011187 glycerol Nutrition 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 125000000542 sulfonic acid group Chemical group 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 108091005804 Peptidases Proteins 0.000 description 10
- 239000004365 Protease Substances 0.000 description 10
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 9
- 239000007791 liquid phase Substances 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 150000004760 silicates Chemical class 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 108010065511 Amylases Proteins 0.000 description 8
- 102000013142 Amylases Human genes 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 235000019418 amylase Nutrition 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002170 ethers Chemical class 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229960003975 potassium Drugs 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 5
- 102000035195 Peptidases Human genes 0.000 description 5
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000004676 glycans Chemical class 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 229920001282 polysaccharide Polymers 0.000 description 5
- 239000005017 polysaccharide Substances 0.000 description 5
- 235000019419 proteases Nutrition 0.000 description 5
- 235000018102 proteins Nutrition 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004382 Amylase Substances 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 108090001060 Lipase Proteins 0.000 description 4
- 102000004882 Lipase Human genes 0.000 description 4
- 239000004367 Lipase Substances 0.000 description 4
- 108090000854 Oxidoreductases Proteins 0.000 description 4
- 102000004316 Oxidoreductases Human genes 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 108010056079 Subtilisins Proteins 0.000 description 4
- 102000005158 Subtilisins Human genes 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 229940025131 amylases Drugs 0.000 description 4
- 239000004599 antimicrobial Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229940079919 digestives enzyme preparation Drugs 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229940094522 laponite Drugs 0.000 description 4
- 235000019421 lipase Nutrition 0.000 description 4
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 4
- 229920005646 polycarboxylate Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 244000303965 Cyamopsis psoralioides Species 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- PGNYGWRFIFYBKV-UHFFFAOYSA-N [Mg].[Li].[Na] Chemical compound [Mg].[Li].[Na] PGNYGWRFIFYBKV-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 108090000637 alpha-Amylases Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000001508 potassium citrate Substances 0.000 description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 235000019351 sodium silicates Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000001226 triphosphate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/043—Liquid or thixotropic (gel) 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/045—Multi-compartment
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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 invention relates to pre-portioned detergent, preferably machine dishwashing detergent, in a water-soluble packaging having at least two compartments, comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably sodium carbonate, in an amount of 20 to 60 wt. -% and further contains a magnesium-containing phyllosilicate in an amount of 0.01 to 10 wt .-%, each based on the total weight of the first liquid preparation contains.
- first liquid preparation alkali metal carbonate, preferably sodium carbonate
- a magnesium-containing phyllosilicate in an amount of 0.01 to 10 wt .-%
- Hard surface cleaners such as dishwashing detergents
- dishwashing detergents are available to the consumer in a variety of forms.
- traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance.
- the consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.
- over- or under-dosing of individual components or of the entire cleaning agent is avoided by the pre-portioning compared to multicomponent liquid or gel-like cleaning agents from multi-chamber bottles.
- liquid detergents often have the problem that the cleaning performance, especially on burnt dirt, is not sufficient. This results from the fact that the liquid pre-portioned detergents often can not contain high amounts of highly alkaline substances, since otherwise the tightness and storability of the pre-portioned detergent in the water-soluble packaging is not guaranteed.
- alkali metal hydroxides or meta-silicates can not be used, since the water-soluble packaging can be at least partially attacked by such ingredients. This results in unwanted leaks or leaks in the water-soluble packaging.
- the WO 02/06438 A1 discloses liquid or gel machine dishwashing detergents comprising sodium carbonate which may also be pre-portioned in water soluble packages.
- the object of the invention was thus to provide liquid pre-portioned machine dishwashing detergents which have an improved cleaning performance and are simultaneously storage-stable.
- the object is achieved by providing a pre-portioned detergent, preferably dishwasher detergent, in a water-soluble packaging with at least two compartments comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably sodium carbonate, in an amount of 20 to 60 wt .-% (based on the total weight of the first liquid preparation) and further comprises a magnesium-containing phyllosilicate in an amount of 0.01 to 10 wt .-%, each based on the total weight of the first liquid preparation contains. contains.
- Liquid as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point.
- Pre-portioned detergents are generally present in a water-soluble packaging, for example a film containing a disposable portion.
- the pre-portioned detergent is in a water-soluble packaging.
- the cleaning agent in particular machine dishwashing detergent, can be made up in such a way that disposable portions are each packed separately.
- the water-soluble packaging allows a portioning of the cleaning agent.
- the amount of total detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g, in particular 17 to 23 g.
- the water-soluble packaging in this case has at least two or more spatially separated compartments (chambers) into which spatially separated at least a first liquid and a second liquid preparation are filled.
- composition which results in combination with the other preparations / phases a cleaning agent, in particular a machine dishwashing detergent.
- the pre-portioned detergent according to the invention contains, in addition to the two preparations mentioned, one or two further preparations in further, separate compartments.
- two liquid and one solid preparation, two liquid and two solid preparations, three or four liquid preparations may be present in a corresponding number of separate compartments.
- a packaging according to the invention with two compartments may preferably be present, the first and the second liquid preparation being present separately from one another in each of the compartments.
- Preferred may be pre-portioned detergents in which the water-soluble package contains, in addition to two or more liquid preparations, one, two or more chambers with solid preparations.
- two or more solid preparations it is preferred that they be of different composition and / or have a different solid form
- the cleaning agent according to the invention in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments.
- the package contains two, three or more chambers, wherein two, three or more of these chambers are filled with liquid preparations, which are preferably different from each other (for example in the weight proportions of individual components), and in particular have one or more different ingredients from each other.
- At least one as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more.
- At least two as used herein means 2 or more, for example, 2, 3, 4, 5, 6 or more.
- the first liquid preparation contains from 20 to 60% by weight of alkali metal carbonate, especially sodium carbonate (Na 2 CO 3 ).
- alkali metal carbonates are not to be understood as meaning alkali metal bicarbonates, such as, for example, sodium bicarbonate, or alkali metal sesquicarbonates.
- the alkali metal carbonates depending on their amount and the water content of the first preparation in solution or as a dispersion available.
- sodium carbonate Due to a lower tendency to separate into dispersions, it may be preferable to use sodium carbonate, in particular in the case of relatively high amounts of alkali metal carbonate in the first preparation or in the case of small amounts of water in the first preparation. It is particularly advantageous when using sodium carbonate, that the incorporation of the alkali reserve in the form of sodium carbonate (soda) is stable in the liquid preparation.
- alkali metal carbonates e.g. Sodium carbonate and potassium carbonate, or sodium carbonate and lithium carbonate are used.
- the amounts stated below then apply to the total amount of alkali metal carbonates used in the first liquid preparation. It is preferred to use a single alkali metal carbonate, especially sodium carbonate.
- alkali metal carbonate preferably sodium carbonate (soda)
- the second liquid preparation may also be contained in the second liquid preparation (and optionally in further preparations) alkali metal carbonate, but it is preferred that the second liquid preparation (or if given also all other preparations (ie all preparations contained in the pre-portioned detergent except the first preparation ) is substantially free of alkali metal carbonate.
- Substantially free of alkali metal carbonate means that the second (and possibly the other, separated from the first preparation) preparations, less than 10 wt .-%, in particular less than 5 wt .-%, preferably less than 1 wt .-%, in particular less than 0.5 wt .-%, alkali metal carbonate (in each case based on the weight of the individual preparation).
- alkali metal carbonate preferably sodium carbonate (soda)
- the total amount of the alkali metal carbonate, preferably of the alkali metal carbonate, in particular of the sodium carbonate (soda), per detergent portion is 1 to 3 g, in particular 1.5 to 2.5 g.
- the said total amount of 1 to 3 g of alkali metal carbonate, in particular sodium carbonate (soda) may also be the total amount per job (ie the total amount of cleaning agent used in a complete cleaning program of a dishwashing machine).
- the ratio of alkali metal carbonate to water in the first liquid preparation is based in each case on the total amount of the first liquid Preparation preferably between 7: 1 and 1: 1, in particular between 6: 1 and 2: 1, particularly preferably between 5: 1 and 3: 1. This ratio applies in particular to the weight ratio of sodium carbonate (soda) to water.
- the first liquid preparation is preferably low in water.
- Low-water as used herein means that the first liquid preparation contains less than 20% by weight of water, more preferably less than 15% by weight of water, most preferably less than 13% by weight of water (based on the total weight of water) first liquid phase).
- the water content as defined herein refers to the water content determined by Karl Fischer titration.
- the low-water first liquid preparation preferably contains from 5 to 12% by weight of water. (based on the total weight of the first liquid phase).
- the weight ratio of alkali metal carbonate, in particular sodium carbonate (soda) to water between 7: 1 and 2: 1 is in particular between 6: 1 and 2.5: 1, particularly preferably between 5: 1 and 3: 1.
- a magnesium-containing phyllosilicate preferably sodium-magnesium-containing phyllosilicates, very particularly a Li-Na-Mg phyllosilicate
- phyllosilicates in particular magnesium-containing phyllosilicate, preferably sodium-magnesium-containing phyllosilicates, preferably prepared synthetically, are suitable for achieving formation of a stable and storage-stable dispersion of the large amount of alkali metal carbonate without a.
- Demixing takes place.
- These phyllosilicates, in particular the lithium-magnesium-sodium phyllosilicates have the effect that no separation of different liquid phases or sedimentation of solid constituents takes place in the first liquid preparation.
- LaponiteĀ® magnesium or sodium magnesium phyllosilicates BYK Additives GmbH in particular the LaponiteĀ® RD or LaponiteĀ® RDS, or the OptigelĀ® SH.
- Particularly preferred phyllosilicates are lithium-magnesium-sodium phyllosilicates, for example available under the trade name LaponiteĀ® RD, which are particularly suitable for ensuring the stability of the dispersion of the alkali metal carbonates in the first liquid preparation over an extended period of time, during storage.
- the phyllosilicates can also serve to thicken or to adjust the viscosity of the first liquid preparation.
- the layered silicate is in the first liquid preparation to 0.01 to 10 wt .-%, preferably 0.1 to 8 wt .-%, in particular 0.3 to 5 wt .-%, most preferably 0.6 to 3 wt .-% (active substance, in each case based on the total weight of the first liquid preparation).
- concentrations mentioned are low enough to avoid increased deposit formation on the surfaces to be cleaned, for example the dishes or the glasses.
- the detergents prepared according to the invention preferably further comprise at least one nonionic surfactant.
- one or more nonionic surfactants may be present in the first and / or in the second (and further liquid) preparations. Preference is given to using at least one nonionic surfactant which is a rinse aid surfactant which positively influences the rinse aid result (after the end of the dishwashing program).
- first and / or the second liquid preparation can be used in the first and / or the second liquid preparation. It may be preferable to use a nonionic surfactant other than the second liquid preparation in the first liquid preparation.
- nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
- Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
- the automatic dishwashing detergents contain nonionic surfactants from the group of alkoxylated alcohols which constitute an important group of rinse-action nonionic surfactants (i.e., rinse aid surfactants).
- surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
- Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
- nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
- nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A ''O) z -R 2 , hereinafter also referred to as "hydroxymix ether"
- hydroxymix ether the performance, in particular the rinsing performance, according to the invention Preparations produced significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing only alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
- Such surfactants are therefore also to be understood as rinse aid surfactants in the context of the invention. It may be preferable, in addition to nonionic surfactants from the group of polyakoxylated fatty alcohols, to use the previously mentioned hydroxy mixed ethers.
- Particularly preferred surfactants are of the formula R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
- the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
- nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
- each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
- R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
- R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- each R 3 in the above formula may be different if x ā 2.
- the alkylene oxide unit in the square bracket can be varied.
- the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
- Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
- Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the total cleaning agent preferably 0.1 to 10 wt .-%, preferably 0.5 to 8.0 wt .-% and in particular 1.0 to 4.0 wt .-% is.
- such hydroxy mixed ethers are contained in the first and / or the second liquid preparation. If further preparation is present in the cleaning agent, these may also contain nonionic surfactants, in particular alkoxylated fatty alcohols and / or hydroxy mixed ethers. It may be particularly preferred if the o.g. Hydroxymischether contained in the second liquid preparation.
- the first liquid preparation contains at least one nonionic surfactant, preferably selected from the group of the alkoxylated alcohols, in particular the abovementioned alkoxylated alcohols.
- the first liquid preparation contains between 1 and 75% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight (based in each case on the total weight of the first liquid preparation) of at least one nonionic surfactant. If several nonionic surfactants are included, the aforementioned amount refers to the sum of all nonionic surfactants in the first liquid preparation.
- the first liquid preparation contains 25 to 50% by weight of alkali metal carbonate, preferably sodium carbonate, and 10 to 50% by weight of nonionic surfactant selected from the alkoxylated alcohols, in particular those alkoxylated alcohols of the abovementioned general formula (I) , contains (in each case based on the total weight of the first liquid preparation).
- alkali metal carbonate preferably sodium carbonate
- nonionic surfactant selected from the alkoxylated alcohols in particular those alkoxylated alcohols of the abovementioned general formula (I)
- contains in each case based on the total weight of the first liquid preparation.
- the quantitative ratios given here are based on the sum of all nonionic surfactants selected from the alkoxylated alcohols in the first liquid preparation.
- nonionic surfactants selected above as preferred have the advantage that they are generally liquid to pasty, and in addition to their action as rinse aid surfactant, they can also serve as liquid matrix component (s) in the first liquid preparation.
- the first liquid preparation contains 25 to 50% by weight of alkali metal carbonate, preferably sodium carbonate, and 10 to 50% by weight of at least one of the nonionic surfactants described in the preceding paragraph as being particularly preferred according to formula (I). If a plurality of nonionic surfactants contain the surfactants mentioned as preferred in the preceding paragraph, then the stated amounts relate in each case to the total amount of the nonionic surfactants falling under the preferred formula. Particular preference is given in particular to those combinations which additionally comprise from 0.3 to 5% by weight, preferably from 0.6 to 3% by weight, of a synthetic Li-Na-Mg phyllosilicate.
- nonionic surfactants mentioned in particular those mentioned as being preferred, may also be present (also in addition) in the second liquid preparation.
- the liquid preparations each contain one or more solvents, preferably organic solvents.
- suitable solvents are, for example, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycol, diethylene glycol, alkanolamines, glycerol, and / or mixtures thereof.
- Alkanolamines such as in particular monoethanolamine and triethanolamine, are likewise suitable, although it is preferred that these be present only in small amounts, in particular up to about 5% by weight. otherwise it may impair the integrity of the enveloping package (especially in PVA-containing films).
- Particularly preferred solvents are 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycols (individually or as a mixture), glycerol, and / or a mixture thereof.
- 1,2-propanediol, glycerol or a mixture of 1,2-propanediol and glycerol are especially preferred solvents.
- solvents are suitable which are selected from non-volatile organic solvents.
- Non-volatile organic solvents for the purposes of the present invention have a volatility (also called volatility or evaporation number) of at least 10, and in particular more than 35, on.
- the volatility is given as the ratio of the vapor pressure of the substance under consideration to the vapor pressure of the volatile reference substance diethyl ether at 20 Ā° C and a relative humidity of 65 ā 5%.
- Preferred organic solvents having a volatility of at least 10, and especially greater than 35 include polyhydric alcohols such as 2-methyl-1,3-propanediol, 1,3-propanediol, 1,2-propylene glycol and glycerin.
- those organic solvents, in particular polyhydric alcohols, which have a volatility of more than 50 are preferred.
- organic solvents which have a volatility of less than 10 are completely dispensed with.
- non-volatile solvents are 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycols, glycerol, and / or a mixture thereof.
- 1,2-propanediol, glycerol or a mixture of 1,2-propanediol and glycerol are particularly preferred.
- the ratio of the water content of the first and the second liquid preparations to one another is between 5: 1 and 1: 5, preferably 3 : 1 and 1: 3, preferably between 2: 1 and 1: 2.
- This has the advantage that no too large (in particular optically conspicuous) migrations of the water and / or the solvents occur between the individual liquid preparations via the water-soluble packaging. Visually conspicuous migrations can cause one of the chambers to continue to inflate more fluid is filled while the other chamber loses fluid and thereby shrinks. In particular, the shrinkage leads to visually unsightly pre-portioned cleaning agents that are not accepted by the end user.
- additional builders can be used.
- the additional builders that can be used include, in particular, the zeolites, silicates, bicarbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
- the agents are phosphate-free.
- the crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
- silicates Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
- Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi x O 2x + 1 .yH 2 O, in which x is 2.
- both .beta.- and ā -Natriumdisitik ate Na 2 Si 2 O 5 ā y H 2 O, and further in particular Na-SKS-5 ( ā -Na 2 Si 2 O 5), Na-SKS-7 ( ā -Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 ā H 2 O), Na-SKS-10 (NaHSi 2o5 ā 3 H 2 O, kanemite), Na-SKS-11 (t- Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ā -Na 2 Si 2 O 5 ).
- Machine dishwashing detergents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0, 4 to 10 wt .-%, each based on the total weight of these agents.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- amorphous is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.
- Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
- the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations on crockery and also contribute to the cleaning performance.
- phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate) and corresponding mixed salts (Natriumkaliumtripolyphosphate).
- the agents are phosphate-free.
- phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application
- preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 5 to 80 wt .-%, preferably from 10 to 75 wt .-% and in particular from 12.5 to 70 wt .-%, each based on the weight of the total automatic dishwashing detergent.
- Alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances can likewise be used in addition to the alkali metal carbonates according to the invention, preference being given for the purposes of this invention to the use of the alkali hydrogencarbonates and / or -sequicarbonates, preferably sodium bicarbonate or sodium sesquicarbonate.
- a builder system containing a mixture of tripolyphosphate and sodium carbonate is preferred.
- the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent.
- Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
- the phosphates in particular the polyphosphates, it is also possible to use other builders, such as, for example, zeolites, silicates, and in particular also the sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
- the agent is preferably free of water-insoluble builders and particularly preferably contains no zeolites.
- Particularly suitable silicates are crystalline layered silicates of the general formula NaMSi x O 2 ā + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into account. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
- one of the liquid preparations preferably at least the second liquid preparation, for example the first and the second liquid preparation (and optionally further preparations present in the cleaning agent) further contains at least one builder or co-builder, in particular selected from the group formed from citrate, aminocarboxylates (especially MGDA and / or GLDA), polyphosphates (preferably a tripolyphosphate) as well as phosphonates and mixtures thereof.
- a builder or co-builder in particular selected from the group formed from citrate, aminocarboxylates (especially MGDA and / or GLDA) as well as phosphonates and mixtures thereof.
- organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
- Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
- NTA nitrilotriacetic acid
- the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents.
- citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
- aminocarboxylic acids and / or their salts are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
- MGDA methylglycinediacetic acid
- GLDA glutamic diacetic acid
- IDA iminodiacetic acid
- Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
- polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
- Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
- the detergents may contain, in particular, phosphonates as builder.
- the phosphonate compound is preferably a hydroxyalkane and / or aminoalkane phosphonate used.
- HEDP 1-hydroxyethane-1,1-diphosphonate
- Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
- Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
- the cleaning agents according to the invention contain phosphates, in particular tripolyphosphates, it is preferred that they contain as further constituent preferably one or more builder (s) (builder / cobuilder) in addition to the phosphate-containing builder component.
- the proportion by weight of these additional builders differing from the phosphate-containing builder component in the total weight of the compositions according to the invention is preferably from 0.1 to 10% by weight and in particular from 2 to 7% by weight.
- builders other than the phosphate-containing builder component include in particular those described above as further builders, preferably citrates, phosphonates, MGDA, GLDA, iminodisuccinic acid, iminodiacetic acid, EDDS (ethylenediamine-N, N'-disuccinic acid) or the salts of said acids, other organic Cobuilders and silicates.
- Particularly preferred phosphate-containing detergents contain citrate, for example sodium or potassium citrate, as one of their essential builders other than the phosphate-containing builder component. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of citrate are preferred according to the invention. Additionally or alternatively, particularly preferred phosphate-containing detergents may contain phosphonates, such as HEDP, as a builder other than the phosphate-containing builder component. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of phosphonate, in particular HEDP, are preferred according to the invention.
- the cleaning agents of the invention may further contain a sulfopolymer.
- the sulfopolymer is contained in the second liquid phase.
- the proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 2 to 14 wt .-%, especially from 3 to 12 wt .-%, especially from 4 to 8 wt .-%.
- the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymer (s).
- the sulfopolymers can also be used as solids, for example as granules.
- the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
- the copolymers may have two, three, four or more different monomer units.
- Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
- unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ā -chloroacrylic acid, ā -cyanoacrylic acid, crotonic acid, ā -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
- Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
- the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
- metal ions preferably alkali metal ions and in particular for sodium ions.
- partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
- the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
- the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
- Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
- the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
- Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
- nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ā -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
- the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing
- Monomers 60 to 80 wt .-% the monomers are hereby preferably selected from the aforementioned.
- the detergents may contain alkali metal hydroxides.
- alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
- Alternative cleaning agents according to the invention are free of alkali metal hydroxides.
- the agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances, and antimicrobial agents.
- at least one further constituent preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances, and antimicrobial agents.
- pH stabilizers in particular alkali metal bicarbonate (s)
- dye s
- fragrances / or preservatives
- one of the liquid preparations preferably the second liquid preparation, preferably contains one or more substances selected from the group consisting of pH regulators, anionic, cationic and amphoteric surfactants, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, Electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, perfumes, bitter substances, and antimicrobial agents.
- the second liquid preparation contains one or more substances selected from the group consisting of pH regulators, anionic, cationic and amphoteric surfactants, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, Fragrances, bitter substances, and antimicrobial agents.
- Dyes are preferably present in at least one, preferably in the first and the second liquid preparation, in particular in all preparations.
- Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
- fatty acid cyanamides sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and ā -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
- sulfosuccinates sulfosuccinic esters
- sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters sulfosuccinamates
- the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.
- Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethylbetain and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethylbetain.
- Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix are four identical or different, in particular two long and two short-chain, alkyl radicals and X - are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
- quaternary surface-active compounds in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
- the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
- glass corrosion inhibitors used are polyethyleneimines or zinc salts, preferably zinc salts, in particular zinc acetate. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
- the enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
- Detergents according to the invention preferably contain enzymes in total amounts of from 1 ā 10 -6 to 5% by weight, based on active protein.
- the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
- subtilisin type those of the subtilisin type are preferable.
- these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
- amylases which can be used according to the invention are the ā -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the ā -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
- lipases or cutinases are also usable according to the invention.
- these include, for example, the lipases originally obtainable from, or further developed, Humicola lanuginosa (Thermomyces lanuginosus), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most preferably all of the exchanges D96L, T213R and N233R.
- Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases), can be used according to the invention to increase the bleaching effect.
- peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
- organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
- a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
- damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
- inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
- Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
- Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
- Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
- the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
- further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
- the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
- Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10 Wt .-% of the enzyme protein.
- detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
- the first liquid preparation is substantially free of enzymes.
- substantially free of enzymes means that the first liquid preparation containing the alkali metal carbonate, especially the sodium carbonate, less than 1 wt .-%, in particular less than 0.1 wt .-% enzyme preparation (based on the total weight of the first liquid Preparation).
- the enzymes in particular the amylase (s) and / or protease (s), are preferably used in the second liquid preparation.
- the pH of the cleaning agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application.
- the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5
- the pH-adjusting agents are acids and / or alkalis.
- Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
- Suitable bases are selected from the group of alkali metal hydroxides and alkaline earth metal hydroxides and carbonates, in particular the alkali metal bicarbonates, of which potassium bicarbonate and especially sodium bicarbonate is preferred.
- alkanolamine may also be volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule.
- the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
- the alkanolamine is contained in agents according to the invention preferably in an amount of 0.5 to 5 wt .-%, in particular in an amount of 1 to 4 wt .-%.
- the cleaning agent according to the invention is free of alkanolamine and ammonia.
- the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents).
- buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H 2 O and tripotassium citrate H 2 O.
- Suitable thickeners are all viscosity regulators customarily used in detergents and cleaners, for example organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, Casein), organic modified natural products (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, gum ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides).
- organic natural thickeners agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, Casein
- organic modified natural products carboxymethyl
- polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (US Pat. CTFA): carbomers), also referred to as carboxyvinyl polymers.
- Such polyacrylic acids are available, inter alia, from the company 3V Sigma under the trade name PolygelĀ®, for example PolygelĀ® DA, and from the company BFGoodrich under the trade name CarbopolĀ®, for example CarbopolĀ® 940 (molecular weight about 4,000,000), CarbopolĀ® 941 (Molecular weight about 1,250,000) or CarbopolĀ® 934 (molecular weight about 3,000,000).
- acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C 1-4 -alkanols (INCI acrylates copolymer), such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2 ) or of butyl acrylate and methyl methacrylate ( CAS 25852-37-3 ) and which are available, for example, from Rohm & Haas under the trade names AculynĀ® and AcusolĀ® and from Degussa (Goldschmidt) under the trade name TegoĀ® Polymer, for example the anionic non-associative polymers AculynĀ® 22, AculynĀ® 28, AculonĀ® 33 (cross-linked), AcusolĀ® 810, AcusolĀ® 823 and AcusolĀ® 830 ( CAS 25852-37-3 ).
- CarbopolĀ® for example the hydrophobized CarbopolĀ® ETD 2623 and CarbopolĀ® 1382 (INCI acrylates / C10-30 alkyl acrylate crosspolymer) and CarbopolĀ® AQUA 30 (formerly CarbopolĀ® EX 473).
- CarbopolĀ® ETD 2623 and CarbopolĀ® 1382 ICI acrylates / C10-30 alkyl acrylate crosspolymer
- CarbopolĀ® AQUA 30 now CarbopolĀ® EX 473
- Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
- polysaccharide gums for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
- polysaccharide thickeners such as starches or cellulose derivatives
- starches or cellulose derivatives may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
- starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
- a particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum produced by Xanthomonas campestris and some other species under aerobic conditions having a molecular weight of 2-15 x 10 6 and, for example, by Kelco under the trade names KeltrolĀ® and KelzanĀ® or also available from the company Rhodia under the trade name RhodopolĀ®.
- the second liquid preparation has a viscosity above 1000 mPas directly after preparation (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 Ā° C.), in particular between 2000 and 10000 mPas. After storage, the viscosity may be higher, for example greater than 10,000 mPas, such as in the range 10000-50000 mPas, (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 Ā° C). It is preferable that the second liquid preparation is flowable at room temperature.
- the cleaning agents according to the invention are characterized in that they are stable on storage and even after a prolonged period, no phase separation occurs.
- the water-soluble packaging of the cleaning agent (also referred to as a water-soluble coating) is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
- the package may be formed of one or two or more layers of the water-soluble film material.
- the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
- the water-soluble packaging is a water-soluble packaging made of a polyvinyl alcohol or polyvinyl alcohol copolymer-containing film. It is preferable that the water-soluble packaging contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble packaging containing polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.
- Suitable water-soluble films for preparing the water-soluble packaging are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
- polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
- polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers.
- at least one layer of the water-soluble packaging comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above can be additionally used as a polyvinyl alcohol-containing film material suitable for producing the water-soluble packaging Be added polymers.
- a preferred additional polymer is polylactic acids.
- Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
- Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
- polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
- the film material contains further additives.
- the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, Propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
- Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
- Suitable water-soluble films for use in the water-soluble packaging / water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, M8534, C8400 or M8900.
- Other suitable films include films named SolublonĀ® PT, SolublonĀ® GA, SolublonĀ® KC or SolublonĀ® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
- the cleaning agents according to the invention can be used as dishwashing detergents, in particular automatic dishwashing detergents (machine dishwashing detergents).
- dishwashing detergents machine dishwashing detergents
- the corresponding use is also the subject of the invention.
- the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used.
- the particular embodiments described above also apply to the use or the method.
- the cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.
- Chamber I Chamber II Soda (calcined, anhydrous) 40 - 1,2-propylene glycol 8th 10 sodium 0.5 - Synthetic Li-Na-Mg phyllosilicate 2 - C10-C12 alcohol with EO / PO (nonionic surfactant) 40 - potassium - 20 hydroxy mixed - 2 Acrylic acid polymer, Na salt - 0.5 sulfopolymer - 8th Sodium citrate (dihydrate) - 4 glycerin - 25 ethanolamine - 3 phosphonate - 2 Enzyme preparations, liquid (containing protease, amylase) - 5 Zinc acetate (anhydrous) - 0.2 Perfume, dye, excipients, preservatives 0.5 0.5 water To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100%
- the pre-portioned detergent according to the invention which was provided in a Zweischpouch (two-chamber bag) of PVA-containing film and 5 g of the first liquid phase (chamber I) and 15 g of the second liquid phase (chamber II) contained when used in a conventional Dishwasher a good cleaning performance on burnt stains compared to a commercially available pre-portioned liquid detergent in a Einttingpouch.
- Chamber I Chamber II Soda (calcined, anhydrous) 40 - 1,2-propylene glycol 10 10 sodium 0.5 - Synthetic Li-Na-Mg phyllosilicate - - C10-C12 alcohol with EO / PO (nonionic surfactant) 40 - potassium - 20 hydroxy mixed - 2 Acrylic acid polymer, Na salt - 0.5 sulfopolymer - 8th Sodium citrate (dihydrate) - 4 glycerin - 25 ethanolamine - 3 phosphonate - 2 Enzyme preparations, liquid (containing protease, amylase) - 5 Zinc acetate (anhydrous) - 0.2 Perfume, dye, excipients, preservatives 0.5 0.5 water To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100% To 100%
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Description
Die Erfindung betrifft vorportioniertes Reinigungsmittel, bevorzugt MaschinengeschirrspĆ¼lmittel, in einer wasserlƶslichen Verpackung mit mindestens zwei Kompartimenten, umfassend mindestens eine erste und eine zweite flĆ¼ssige Zubereitung, dadurch gekennzeichnet, dass die erste flĆ¼ssige Zubereitung Alkalimetallcarbonat, bevorzugt Natriumcarbonat, in einer Menge von 20 bis 60 Gew.-% und weiterhin ein Magnesium-haltiges Schichtsilikat in einer Menge von 0,01 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Zubereitung, enthƤlt.The invention relates to pre-portioned detergent, preferably machine dishwashing detergent, in a water-soluble packaging having at least two compartments, comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably sodium carbonate, in an amount of 20 to 60 wt. -% and further contains a magnesium-containing phyllosilicate in an amount of 0.01 to 10 wt .-%, each based on the total weight of the first liquid preparation contains.
Reinigungsmittel fĆ¼r harte OberflƤchen, wie beispielsweise GeschirrspĆ¼lmittel, stehen dem Verbraucher in einer Vielzahl von Angebotsformen zur VerfĆ¼gung. Neben den traditionellen festen Mitteln gewinnen in letzter Zeit zunehmend flieĆfƤhige und insbesondere flĆ¼ssige bis gelfƶrmige Reinigungsmittel an Bedeutung. Der Verbraucher schƤtzt vor allem die schnelle Lƶslichkeit und die damit einhergehende schnelle VerfĆ¼gbarkeit der Inhaltsstoffe in der Reinigungsflotte insbesondere auch in KurzgeschirrspĆ¼lprogrammen und bei niedrigen Temperaturen. AuĆerdem wird durch die Vorportionierung im Vergleich zu mehrkomponentigen flĆ¼ssigen oder gelfƶrmigen Reinigungsmitteln aus Mehrkammerflaschen eine Ćber- oder Unterdosierung einzelner Komponenten bzw. des gesamten Reinigungsmittels vermieden.Hard surface cleaners, such as dishwashing detergents, are available to the consumer in a variety of forms. In addition to the traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance. The consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures. In addition, over- or under-dosing of individual components or of the entire cleaning agent is avoided by the pre-portioning compared to multicomponent liquid or gel-like cleaning agents from multi-chamber bottles.
Ferner haben sich die Verbraucher an ein bequemes Dosieren von vorportionierten maschinellen GeschirrspĆ¼lmitteln gewƶhnt und nutzen diese Produkte bisher vor allem in Form von Tabletten. Um ein flĆ¼ssiges GeschirrspĆ¼lmittel, das die oben erwƤhnten Vorteile gegenĆ¼ber festen Zusammensetzungen bietet, in eine vorportionierte Angebotsform zu bringen, bietet sich die Verwendung von wasserlƶslichen Folien in der Form von Beuteln an. Einmalportionen, insbesondere wasserlƶsliche Beutel erfreuen sich beim Verbraucher nicht nur deshalb zunehmender Beliebtheit, weil der Verbraucher mit der chemischen Zusammensetzung nicht mehr in BerĆ¼hrung kommt, sondern nicht zuletzt auch wegen der attraktiven Optik der Beutel.Further, consumers have become accustomed to conveniently dosing pre-portioned automatic dishwashing detergents and have been using these products primarily in the form of tablets. In order to provide a liquid dishwashing detergent which offers the above-mentioned advantages over solid compositions in a pre-portioned form, the use of water-soluble films in the form of sachets lends itself. Disposable portions, especially water-soluble bags enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag.
Solche flĆ¼ssigen Reinigungsmittel haben allerdings hƤufig das Problem, dass die Reinigungsleistung, insbesondere auf angebranntem Schmutz, nicht ausreichend ist. Dies resultiert daraus, dass die flĆ¼ssigen vorportionierten Reinigungsmittel hƤufig nicht hohe Mengen von hochalkalischen Substanzen enthalten kƶnnen, da sonst die Dichtigkeit und LagerfƤhigkeit des vorportionierten Reinigungsmittels in der wasserlƶslichen Verpackung nicht gewƤhrleistet ist.However, such liquid detergents often have the problem that the cleaning performance, especially on burnt dirt, is not sufficient. This results from the fact that the liquid pre-portioned detergents often can not contain high amounts of highly alkaline substances, since otherwise the tightness and storability of the pre-portioned detergent in the water-soluble packaging is not guaranteed.
Insbesondere grƶĆere Mengen (mehr als 10 Gew-%) an Alkalimetallhydroxiden oder Meta-Silikaten kƶnnen nicht eingesetzt werden, da die wasserlƶsliche Verpackung durch solche Inhaltsstoffe zumindest teilweise angegriffen werden kann. Dadurch entstehen nicht gewollte Leckagen oder Undichtigkeiten der wasserlƶslichen Verpackung. Ćhnliches gilt fĆ¼r grƶĆere Mengen von aliphatischen Aminen, insbesondere von Diethylentriamin. Ortho-Silikate in grƶĆeren Mengen sind ebenfalls nicht erwĆ¼nscht, da diese zu starken BelƤgen auf dem SpĆ¼lgut fĆ¼hren.In particular, larger amounts (more than 10% by weight) of alkali metal hydroxides or meta-silicates can not be used, since the water-soluble packaging can be at least partially attacked by such ingredients. This results in unwanted leaks or leaks in the water-soluble packaging. The same applies to larger amounts of aliphatic amines, in particular of diethylenetriamine. Ortho-silicates in larger quantities are also undesirable because they lead to strong deposits on the items to be washed.
Die
Die Aufgabe der Erfindung bestand also darin, flĆ¼ssige vorportionierte MaschinengeschirrspĆ¼lmittel bereitzustellen, die eine verbesserte Reinigungsleistung aufweisen und die gleichzeitig lagerstabil sind.The object of the invention was thus to provide liquid pre-portioned machine dishwashing detergents which have an improved cleaning performance and are simultaneously storage-stable.
Die Aufgabe wird gelƶst durch die Bereitstellung eines vorportionierten Reinigungsmittels, bevorzugt MaschinengeschirrspĆ¼lmittels, in einer wasserlƶslichen Verpackung mit mindestens zwei Kompartimenten, umfassend mindestens eine erste und eine zweite flĆ¼ssige Zubereitung, dadurch gekennzeichnet, dass die erste flĆ¼ssige Zubereitung Alkalimetallcarbonat, bevorzugt Natriumcarbonat, in einer Menge von 20 bis 60 Gew.-% (bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Zubereitung) und weiterhin ein Magnesium-haltiges Schichtsilikat in einer Menge von 0,01 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Zubereitung, enthƤlt.enthƤlt.The object is achieved by providing a pre-portioned detergent, preferably dishwasher detergent, in a water-soluble packaging with at least two compartments comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably sodium carbonate, in an amount of 20 to 60 wt .-% (based on the total weight of the first liquid preparation) and further comprises a magnesium-containing phyllosilicate in an amount of 0.01 to 10 wt .-%, each based on the total weight of the first liquid preparation contains. contains.
"FlĆ¼ssig", wie hierin in Bezug auf das erfindungsgemƤĆe Reinigungsmittel verwendet, schlieĆt alle flieĆfƤhigen Zusammensetzungen ein und erfasst insbesondere auch Gele und pastƶse Zusammensetzungen. Insbesondere schlieĆt der Begriff auch Nicht-Newtonsche FlĆ¼ssigkeiten, die eine FlieĆgrenze besitzen, ein."Liquid" as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point.
Vorportionierte Reinigungsmittel liegen in der Regel in einer wasserlƶslichen Verpackung, beispielsweise einer Folie, die eine Einmalportion enthƤlt, vor.Pre-portioned detergents are generally present in a water-soluble packaging, for example a film containing a disposable portion.
Das vorportionierte Reinigungsmittel befindet sich in einer wasserlƶslichen Verpackung. Das Reinigungsmittel, insbesondere MaschinengeschirrspĆ¼lmittel, kann dabei derart konfektioniert sein, dass Einmalportionen jeweils separat verpackt sind. Die wasserlƶsliche Verpackung erlaubt eine Portionierung des Reinigungsmittels. Die Menge an gesamtem Reinigungsmittel in der Portionspackung betrƤgt vorzugsweise 5 bis 50 g, besonders bevorzugt 10 bis 30 g, vor allem 15 bis 25 g, insbesondere 17 bis 23 g.The pre-portioned detergent is in a water-soluble packaging. The cleaning agent, in particular machine dishwashing detergent, can be made up in such a way that disposable portions are each packed separately. The water-soluble packaging allows a portioning of the cleaning agent. The amount of total detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g, in particular 17 to 23 g.
Die wasserlƶsliche Verpackung weist dabei mindestens zwei oder mehr voneinander rƤumlich getrennte Kompartimente (Kammern) auf, in die rƤumlich getrennt mindestens eine erste flĆ¼ssige und eine zweite flĆ¼ssige Zubereitung gefĆ¼llt werden.The water-soluble packaging in this case has at least two or more spatially separated compartments (chambers) into which spatially separated at least a first liquid and a second liquid preparation are filled.
Insbesondere geeignet sind Zweikammerbeutel, die eine erste flĆ¼ssige Zubereitung und eine zweite flĆ¼ssige Zubereitung in getrennten Kompartimenten enthalten. Als Zubereitung (Phase) wird hier eine Reinigungsmittel(teil-)zusammensetzung verstanden, die in Kombination mit der bzw. den anderen Zubereitungen/Phasen ein Reinigungsmittel, insbesondere ein MaschinengeschirrspĆ¼lmittel ergibt.Particularly suitable are two-compartment bags which contain a first liquid preparation and a second liquid preparation in separate compartments. As preparation (phase) becomes Here, a detergent (partial) composition understood, which results in combination with the other preparations / phases a cleaning agent, in particular a machine dishwashing detergent.
Es kann insbesondere bevorzugt sein, dass das erfindungsgemƤĆe vorportionierte Reinigungsmittel neben den zwei erwƤhnten Zubereitungen ein oder zwei weitere Zubereitungen in weiteren, voneinander getrennten Kompartimenten enthƤlt. Beispielswiese kƶnnen zwei flĆ¼ssige und eine feste Zubereitung, zwei flĆ¼ssige und zwei feste Zubereitungen, drei oder vier flĆ¼ssige Zubereitungen in entsprechend vielen voneinander getrennten Kompartimenten vorliegen.It may be particularly preferred that the pre-portioned detergent according to the invention contains, in addition to the two preparations mentioned, one or two further preparations in further, separate compartments. For example, two liquid and one solid preparation, two liquid and two solid preparations, three or four liquid preparations may be present in a corresponding number of separate compartments.
Bevorzugt kann eine erfindungsgemƤĆe Verpackung mit zwei Kompartimenten vorliegen, wobei die erste und die zweite flĆ¼ssige Zubereitung getrennt voneinander in jeweils einem der Kompartimente vorliegen.A packaging according to the invention with two compartments may preferably be present, the first and the second liquid preparation being present separately from one another in each of the compartments.
Bevorzugt kƶnnen vorportionierte Reinigungsmittel sein, bei denen die wasserlƶsliche Verpackung zusƤtzlich zu zwei oder mehr flĆ¼ssigen Zubereitungen, eine, zwei oder mehr Kammern mit festen Zubereitungen beinhaltet. Wenn zwei oder mehr feste Zubereitungen vorgesehen sind, ist es bevorzugt, dass diese von unterschiedlicher Zusammensetzung sind und/oder eine andere feste Form aufweisenPreferred may be pre-portioned detergents in which the water-soluble package contains, in addition to two or more liquid preparations, one, two or more chambers with solid preparations. When two or more solid preparations are provided, it is preferred that they be of different composition and / or have a different solid form
Das erfindungsgemƤĆe Reinigungsmittel, insbesondere MaschinengeschirrspĆ¼lmittel, kann auch in einer wasserlƶslichen Verpackung vorliegen, die insbesondere mehr als zwei, also beispielsweise drei, vier, fĆ¼nf oder sechs Kompartimente enthƤlt. Bevorzugt enthƤlt die Verpackung zwei, drei oder mehr Kammern, wobei zwei, drei oder mehr dieser Kammern mit flĆ¼ssigen Zubereitungen gefĆ¼llt sind, die bevorzugt voneinander verschieden sind (beispielsweise in den Gewichtsanteilen einzelner Komponenten), und insbesondere ein oder mehrere voneinander verschiedene Inhaltsstoffe aufweisen.The cleaning agent according to the invention, in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments. Preferably, the package contains two, three or more chambers, wherein two, three or more of these chambers are filled with liquid preparations, which are preferably different from each other (for example in the weight proportions of individual components), and in particular have one or more different ingredients from each other.
"Mindestens ein", wie hierin verwendet, bedeutet 1 oder mehr, beispielsweise 1, 2, 3, 4, 5, oder mehr. "Mindestens zwei" wie hierin verwendet, bedeuten entsprechend 2 oder mehr, beispielsweise 2, 3, 4, 5, 6 oder mehr."At least one" as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more. "At least two" as used herein means 2 or more, for example, 2, 3, 4, 5, 6 or more.
Die erste flĆ¼ssige Zubereitung enthƤlt 20 bis 60 Gew.-% Alkalimetallcarbonat, insbesondere Natriumcarbonat (Na2CO3). AuĆer oder statt Natriumcarbonat kƶnnen auch Kaliumcarbonat oder Lithiumcarbonat eingesetzt werden. Nicht als Alkalimetallcarbonate im Sinne der vorliegenden Erfindung sind Alkalimetallhydrogencarbonate, wie z.B. Natriumhydrogencarbonat, oder Alkalimetallsesquicarbonate, aufzufassen. Die Alkalimetallcarbonate kƶnnen in AbhƤngigkeit von ihrer Menge und dem Wassergehalt der ersten Zubereitung in Lƶsung oder als Dispersion vorliegen. Aufgrund einer geringeren Separationsneigung in Dispersionen kann es bevorzugt sein, insbesondere bei hƶheren Mengen Alkalimetallcarbonat in der ersten Zubereitung oder bei geringen Wassermengen in der ersten Zubereitung, Natriumcarbonat einzusetzen. Besonders vorteilhaft ist bei der Verwendung von Natriumcarbonat, dass die Einarbeitung der Alkalireserve in Form von Natriumcarbonat (Soda) in der flĆ¼ssigen Zubereitung stabil ist.The first liquid preparation contains from 20 to 60% by weight of alkali metal carbonate, especially sodium carbonate (Na 2 CO 3 ). In addition to or instead of sodium carbonate, it is also possible to use potassium carbonate or lithium carbonate. For the purposes of the present invention, alkali metal carbonates are not to be understood as meaning alkali metal bicarbonates, such as, for example, sodium bicarbonate, or alkali metal sesquicarbonates. The alkali metal carbonates, depending on their amount and the water content of the first preparation in solution or as a dispersion available. Due to a lower tendency to separate into dispersions, it may be preferable to use sodium carbonate, in particular in the case of relatively high amounts of alkali metal carbonate in the first preparation or in the case of small amounts of water in the first preparation. It is particularly advantageous when using sodium carbonate, that the incorporation of the alkali reserve in the form of sodium carbonate (soda) is stable in the liquid preparation.
Es kƶnnen auch Mischungen von verschiedenen Alkalimetallcarbonaten, z.B. Natriumcarbonat und Kaliumcarbonat, oder Natriumcarbonat und Lithiumcarbonat eingesetzt werden. Die im weiteren angegebenen Mengen gelten dann fĆ¼r die eingesetzte Gesamtmenge an Alkalimetallcarbonaten in der ersten flĆ¼ssigen Zubereitung. Es ist bevorzugt, ein einzelnes Alkalimetallcarbonat, insbesondere Natriumcarbonat, einzusetzen.Mixtures of various alkali metal carbonates, e.g. Sodium carbonate and potassium carbonate, or sodium carbonate and lithium carbonate are used. The amounts stated below then apply to the total amount of alkali metal carbonates used in the first liquid preparation. It is preferred to use a single alkali metal carbonate, especially sodium carbonate.
Bevorzugt ist es, 20 bis 60 Gew.-%, bevorzugt 25 bis 50 Gew.-%, insbesondere 30 bis 45 Gew.-% Alkalimetallcarbonat, bevorzugt Natriumcarbonat (Soda), in der ersten flĆ¼ssigen Zubereitung einzusetzen.It is preferred to use from 20 to 60% by weight, preferably from 25 to 50% by weight, in particular from 30 to 45% by weight, of alkali metal carbonate, preferably sodium carbonate (soda), in the first liquid preparation.
Es kann auch in der zweiten flĆ¼ssigen Zubereitung (sowie ggf. in weiteren Zubereitungen) Alkalimetallcarbonat enthalten sein, allerdings ist es bevorzugt, dass die zweite flĆ¼ssige Zubereitung (oder falls gegeben auch alle weiteren Zubereitungen (also alle im vorportionierten Reinigungsmittel auĆer der ersten Zubereitung enthaltenen Zubereitungen) im wesentlichen frei von Alkalimetallcarbonat ist.It may also be contained in the second liquid preparation (and optionally in further preparations) alkali metal carbonate, but it is preferred that the second liquid preparation (or if given also all other preparations (ie all preparations contained in the pre-portioned detergent except the first preparation ) is substantially free of alkali metal carbonate.
"Im wesentlichen frei von" Alkalimetallcarbonat bedeutet, dass die zweite (ggf. auch die weiteren, von der ersten Zubereitung getrennten), Zubereitungen, weniger als 10 Gew.-%, insbesondere weniger als 5 Gew.-%, bevorzugt weniger als 1 Gew.-% , insbesondere weniger als 0,5 Gew.-% , Alkalimetallcarbonat (jeweils bezogen auf das Gewicht der einzelnen Zubereitung) enthalten."Substantially free of" alkali metal carbonate means that the second (and possibly the other, separated from the first preparation) preparations, less than 10 wt .-%, in particular less than 5 wt .-%, preferably less than 1 wt .-%, in particular less than 0.5 wt .-%, alkali metal carbonate (in each case based on the weight of the individual preparation).
Insbesondere bevorzugt ist es, 20 bis 60 Gew.-%, bevorzugt 25 bis 50 Gew.-%, insbesondere 30 bis 45 Gew.-% Alkalimetallcarbonat, bevorzugt Natriumcarbonat (Soda), in der ersten flĆ¼ssigen Zubereitung einzusetzen, mit der MaĆgabe, dass die Gesamtmenge des Alkalimetallcarbonats, bevorzugt des Alkalimetallcarbonats, insbesondere des Natriumcarbonats (Soda), pro Reinigungsmittelportion 1 bis 3 g, insbesondere 1,5 bis 2,5 g betrƤgt. Die genannte Gesamtmenge von 1 bis 3 g Alkalimetallcarbonat, insbesondere Natriumcarbonat (Soda), kann auch die Gesamtmenge pro Job betragen, (also die in einem vollstƤndigen Reinigungsprogramm einer GeschirrspĆ¼lmaschine eingesetzte Gesamtmenge des Reinigungsmittels).Particular preference is given to using 20 to 60% by weight, preferably 25 to 50% by weight, in particular 30 to 45% by weight, of alkali metal carbonate, preferably sodium carbonate (soda), in the first liquid preparation, with the proviso that the total amount of the alkali metal carbonate, preferably of the alkali metal carbonate, in particular of the sodium carbonate (soda), per detergent portion is 1 to 3 g, in particular 1.5 to 2.5 g. The said total amount of 1 to 3 g of alkali metal carbonate, in particular sodium carbonate (soda), may also be the total amount per job (ie the total amount of cleaning agent used in a complete cleaning program of a dishwashing machine).
GemĆ¤Ć einer bevorzugten AusfĆ¼hrungsform betrƤgt das VerhƤltnis Alkalimetallcarbonat zu Wasser in der ersten flĆ¼ssigen Zubereitung bezogen jeweils auf die Gesamtmenge der ersten flĆ¼ssigen Zubereitung bevorzugt zwischen 7:1 und 1:1 insbesondere zwischen 6:1 und 2:1, besonders bevorzugt zwischen 5:1 und 3:1. Dieses VerhƤltnis gilt insbesondere fĆ¼r das GewichtsverhƤltnis von Natriumcarbonat (Soda) zu Wasser.According to a preferred embodiment, the ratio of alkali metal carbonate to water in the first liquid preparation is based in each case on the total amount of the first liquid Preparation preferably between 7: 1 and 1: 1, in particular between 6: 1 and 2: 1, particularly preferably between 5: 1 and 3: 1. This ratio applies in particular to the weight ratio of sodium carbonate (soda) to water.
In einer bevorzugten AusfĆ¼hrungsform ist die erste flĆ¼ssige Zubereitung bevorzugt wasserarm. "Wasserarm" wie hierin verwendet, bedeutet, dass die erste flĆ¼ssige Zubereitung weniger als 20 Gew.-% Wasser, insbesondere weniger als 15 Gew.-% Wasser, ganz besonders bevorzugt weniger als 13 Gew.-% Wasser (bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Phase) enthƤlt. Der Wassergehalt wie hierin definiert bezieht sich auf den mittels der Karl Fischer Titration ermittelten Wassergehalt.In a preferred embodiment, the first liquid preparation is preferably low in water. "Low-water" as used herein means that the first liquid preparation contains less than 20% by weight of water, more preferably less than 15% by weight of water, most preferably less than 13% by weight of water (based on the total weight of water) first liquid phase). The water content as defined herein refers to the water content determined by Karl Fischer titration.
Bevorzugt enthƤlt die wasserarme erste flĆ¼ssige Zubereitung 5 bis 12 Gew.-% Wasser. (bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Phase).The low-water first liquid preparation preferably contains from 5 to 12% by weight of water. (based on the total weight of the first liquid phase).
Ćberraschenderweise wurde gefunden, dass in solchen wasserarmen flĆ¼ssigen Zubereitungen, insbesondere solchen mit weniger als 15 Gew.-%, bevorzugt weniger als 13 Gew.-% Wasser, auch grƶĆere Mengen, insbesondere 25 bis 50 Gew.-%, insbesondere 30 bis 45 Gew.-% Alkalimetallcarbonat, insbesondere Natriumcarbonat (Soda), stabil eingearbeitet (insbesondere dispergiert) werden kann, ohne, dass es wƤhrend einer Lagerung zu einer Sedimentation von Feststoffen oder einer Entmischung der flĆ¼ssigen Phase kommt.Surprisingly, it has been found that in such low-water liquid preparations, in particular those having less than 15 wt .-%, preferably less than 13 wt .-% water, even larger amounts, in particular 25 to 50 wt .-%, in particular 30 to 45 wt % Alkali metal carbonate, in particular sodium carbonate (soda), can be stably incorporated (in particular dispersed) without there being any sedimentation of solids or segregation of the liquid phase during storage.
Dies hat den Vorteil, dass bei einem solchermaĆen gewƤhlten VerhƤltnis von Alkalimetallcarbonat zu Wasser in der ersten flĆ¼ssigen Zubereitung, eine Migration von Wasser aus der zweiten flĆ¼ssigen Zubereitung minimiert wird.This has the advantage that with such a selected ratio of alkali metal carbonate to water in the first liquid preparation, migration of water from the second liquid preparation is minimized.
GemĆ¤Ć einer besonders bevorzugten AusfĆ¼hrungsform der wasserarmen ersten flĆ¼ssigen Zubereitung betrƤgt das GewichtsverhƤltnis von Alkalimetallcarbonat, insbesondere Natriumcarbonat (Soda) zu Wasser.zwischen 7:1 und 2:1 insbesondere zwischen 6:1 und 2,5:1, besonders bevorzugt zwischen 5:1 und 3:1.According to a particularly preferred embodiment of the low-water first liquid preparation, the weight ratio of alkali metal carbonate, in particular sodium carbonate (soda) to water, between 7: 1 and 2: 1 is in particular between 6: 1 and 2.5: 1, particularly preferably between 5: 1 and 3: 1.
Weiterhin ist in der ersten flĆ¼ssigen Zubereitung ein Magnesiumhaltige-Schichtsilikat, bevorzugt Natrium-Magnesium-haltige Schichtsilikate, ganz besonders ein Li-Na-Mg-Schichtsilikat, enthalten.
Es wurde nun gefunden, dass Schichtsilikate, insbesondere Magnesiumhaltige Schichtsilikat, bevorzugt Natrium-Magnesium-haltige Schichtsilikate, vorzugsweise synthetisch hergestellt, dazu geeignet sind, eine Bildung einer stabilen und auch lagerstabilen Dispersion der groĆen Alkalimetallcarbonatmenge zu erreichen, ohne dass wƤhrend der Lagerung des Mittels eine Entmischung stattfindet. Diese Schichtsilikate, insbesondere die Lithium-Magnesium-Natrium-Schichtsilikate, bewirken, dass in der ersten flĆ¼ssigen Zubereitung weder eine Entmischung von unterschiedlichen flĆ¼ssigen Phasen noch eine Sedimentation von festen Bestandteilen erfolgt.Furthermore, a magnesium-containing phyllosilicate, preferably sodium-magnesium-containing phyllosilicates, very particularly a Li-Na-Mg phyllosilicate, is contained in the first liquid preparation.
It has now been found that phyllosilicates, in particular magnesium-containing phyllosilicate, preferably sodium-magnesium-containing phyllosilicates, preferably prepared synthetically, are suitable for achieving formation of a stable and storage-stable dispersion of the large amount of alkali metal carbonate without a. During storage of the agent Demixing takes place. These phyllosilicates, in particular the lithium-magnesium-sodium phyllosilicates, have the effect that no separation of different liquid phases or sedimentation of solid constituents takes place in the first liquid preparation.
Hierzu zƤhlen beispielsweise die unter dem Handelsnamen LaponiteĀ® erhƤltlichen Magnesium- oder Natrium-Magnesium- Schichtsilikate der Firma BYK Additives GmbH, insbesondere das LaponiteĀ® RD oder auch LaponiteĀ® RDS, oder das OptigelĀ® SH.These include, for example, available under the trade name LaponiteĀ® magnesium or sodium magnesium phyllosilicates BYK Additives GmbH, in particular the LaponiteĀ® RD or LaponiteĀ® RDS, or the OptigelĀ® SH.
Besonders bevorzugte Schichtsilikate sind Lithium-Magnesium-Natrium-Schichtsilikate, beispielsweise erhƤltlich unter dem Handelsnamen LaponiteĀ® RD, welche besonders geeignet sind, die StabilitƤt der Dispersion der Alkalimetallcarbonate in der ersten flĆ¼ssigen Zubereitung auch Ć¼ber einen lƤngeren Zeitraum, bei Lagerung, zu gewƤhrleisten. DarĆ¼ber hinaus kƶnnen die Schichtsilikate auch zu einer Verdickung bzw. zur Einstellung der ViskositƤt der ersten flĆ¼ssigen Zubereitung dienen.Particularly preferred phyllosilicates are lithium-magnesium-sodium phyllosilicates, for example available under the trade name LaponiteĀ® RD, which are particularly suitable for ensuring the stability of the dispersion of the alkali metal carbonates in the first liquid preparation over an extended period of time, during storage. In addition, the phyllosilicates can also serve to thicken or to adjust the viscosity of the first liquid preparation.
Das Schichtsilikat ist in der ersten flĆ¼ssigen Zubereitung zu 0,01 bis 10 Gew.-%, bevorzugt 0,1 bis 8 Gew.-%, insbesondere 0,3 bis 5 Gew.-%, ganz besonders bevorzugt 0,6 bis 3 Gew.-% (Aktivsubstanz, jeweils bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Zubereitung) enthalten. Die genannten Konzentrationen sind gering genug, um stƤrkere Belagsbildung auf den zu reinigenden OberflƤchen, beispielsweise dem Geschirr oder den GlƤsern zu vermeiden.The layered silicate is in the first liquid preparation to 0.01 to 10 wt .-%, preferably 0.1 to 8 wt .-%, in particular 0.3 to 5 wt .-%, most preferably 0.6 to 3 wt .-% (active substance, in each case based on the total weight of the first liquid preparation). The concentrations mentioned are low enough to avoid increased deposit formation on the surfaces to be cleaned, for example the dishes or the glasses.
Die erfindungsgemĆ¤Ć hergestellten Reinigungsmittel enthalten vorzugsweise weiterhin mindestens ein nichtionisches Tensid. In den erfindungsgemƤĆen Reinigungsmitteln kƶnnen in der ersten und/oder in der zweiten (sowie weiteren flĆ¼ssigen) Zubereitungen ein oder mehrere nichtionische Tenside enthalten sein. Bevorzugt wird dabei mindestens ein nichtionisches Tensid eingesetzt werden, das ein KlarspĆ¼ltensid ist, welches das KlarspĆ¼lergebnis (nach Ende des GeschirrspĆ¼lreinigungsprogramms) positiv beeinflusst.The detergents prepared according to the invention preferably further comprise at least one nonionic surfactant. In the cleaning agents according to the invention, one or more nonionic surfactants may be present in the first and / or in the second (and further liquid) preparations. Preference is given to using at least one nonionic surfactant which is a rinse aid surfactant which positively influences the rinse aid result (after the end of the dishwashing program).
Diese kƶnnen in der ersten und/oder der zweiten flĆ¼ssigen Zubereitung eingesetzt werden. Es kann bevorzugt sein, in der ersten flĆ¼ssigen Zubereitung ein anderes nichtionisches Tensid als in der zweiten flĆ¼ssigen Zubereitung einzusetzen.These can be used in the first and / or the second liquid preparation. It may be preferable to use a nonionic surfactant other than the second liquid preparation in the first liquid preparation.
Als nichtionische Tenside kƶnnen alle dem Fachmann bekannten nichtionischen Tenside eingesetzt werden. Bevorzugt werden schwachschƤumende nichtionische Tenside eingesetzt, insbesondere alkoxylierte, vor allem ethoxylierte, schwach schƤumende nichtionische Tenside. Mit besonderem Vorzug enthalten die maschinellen GeschirrspĆ¼lmittel nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole, die eine wichtige Gruppe von nichtionischen Tensiden mit KlarspĆ¼lwirkung (d.h. KlarspĆ¼ltenside) darstellen.As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. Most preferably, the automatic dishwashing detergents contain nonionic surfactants from the group of alkoxylated alcohols which constitute an important group of rinse-action nonionic surfactants (i.e., rinse aid surfactants).
Bevorzugt einzusetzende Tenside stammen aus den Gruppen der alkoxylierten Niotenside, insbesondere der ethoxylierten primƤren Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen ((PO/EO/PO)-Tenside). Solche (PO/EO/PO)-Niotenside zeichnen sich darĆ¼ber hinaus durch gute Schaumkontrolle aus.Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
Als besonders bevorzugte Niotenside haben sich im Rahmen der vorliegenden Erfindung schwach schƤumende Niotenside erwiesen, welche alternierende Ethylenoxid-(EO) und Alkylenoxideinheiten (AO) aufweisen. Diese Tenside zeigen eine gute Wirkung als KlarspĆ¼ltenside. Unter diesen sind wiederum Tenside mit EO-AO-EO-AO-Blƶcken bevorzugt, wobei jeweils eine bis zehn EO- bzw. AO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Hier sind nichtionische Tenside der folgenden Formel (I)
āāāāāāāāR1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
- wobei R1 ausgewƤhlt ist aus geradkettigen oder verzweigten, gesƤttigten C6-24-Alkylresten;
- R2 und R4 gleich -H, R3 und R5 gleich -CH3 sind,
- R6 ausgewƤhlt ist aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, -CH2CH(CH3)2, -C(CH3)3, C5-20-Alkyl (linear oder verzweigt),
- und die Indizes w, x, y, z unabhƤngig voneinander fĆ¼r ganze Zahlen von 1 bis 6 stehen.
R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
- wherein R 1 is selected from straight-chain or branched, saturated C 6-24 alkyl radicals;
- R 2 and R 4 are -H, R 3 and R 5 are -CH 3 ,
- R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -C (CH 3 ) 3 , C 5-20 alkyl (linear or branched),
- and the indices w, x, y, z are independently integers from 1 to 6.
Somit sind insbesondere nichtionische Tenside bevorzugt, die einen C9-15-Alkylrest mit 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten, gefolgt von 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten aufweisen.Thus, particularly preferred are nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
Bevorzugte nichtionische Tenside sind hierbei solche der allgemeinen Formel R1-CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A'''O)z-R2, in der
- R1 fĆ¼r einen geradkettigen oder verzweigten, gesƤttigten oder ein- bzw. mehrfach ungesƤttigten C6-24-Alkyl- oder -Alkenylrest steht;
- R2 fĆ¼r H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- A, A', A" und A''' unabhƤngig voneinander fĆ¼r einen Rest aus der Gruppe -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-,-CH2-CH(CH2-CH3) stehen,
- w, x, y und z fĆ¼r Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein kƶnnen.
- R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
- R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- A, A ', A "and A''' are independently a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ),
- w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
Durch den Zusatz der vorgenannten nichtionischen Tenside der allgemeinen Formel R1-CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A'''O)z-R2, nachfolgend auch als "Hydroxymischether" bezeichnet, kann die Leistung, insbesondere die KlarspĆ¼lleistung, der erfindungsgemĆ¤Ć hergestellten Zubereitungen deutlich verbessert werden und zwar sowohl im Vergleich zu Tensidfreien System wie auch im Vergleich zu Systemen, die nur alternative nichtionischen Tenside, beispielsweise aus der Gruppe der polyalkoxylierten Fettalkohole enthalten. Solche Tenside sind daher ebenfalls als KlarspĆ¼ltenside im Sinne der Erfindung aufzufassen. Es kann bevorzugt sein, zusƤtzlich zu nichtionischen Tensiden aus der Gruppe der polyakoxylierten Fettalkohole, die zuvor bezeichneten Hydroxymischether einzusetzen.By the addition of the aforementioned nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A '''O) z -R 2 , hereinafter also referred to as "hydroxymix ether", the performance, in particular the rinsing performance, according to the invention Preparations produced significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing only alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols. Such surfactants are therefore also to be understood as rinse aid surfactants in the context of the invention. It may be preferable, in addition to nonionic surfactants from the group of polyakoxylated fatty alcohols, to use the previously mentioned hydroxy mixed ethers.
Bevorzugt werden insbesondere solche endgruppenverschlossene, poly(oxyalkylierten) Niotenside, die, gemĆ¤Ć der Formel R1O[CH2CH2O]xCH2CH(OH)R2, neben einem Rest R1, welcher fĆ¼r lineare oder verzweigte, gesƤttigte oder ungesƤttigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesƤttigten oder ungesƤttigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R2 mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei x fĆ¼r Werte zwischen 1 und 90, vorzugsweise fĆ¼r Werte zwischen 30 und 80 und insbesondere fĆ¼r Werte zwischen 30 und 60 steht.Preference is given in particular to those end-capped, poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
Besonders bevorzugt sind Tenside der Formel R1O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2, in der R1 fĆ¼r einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 18 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x fĆ¼r Werte zwischen 0,5 und 1,5 sowie y fĆ¼r einen Wert von mindestens 15 steht.Particularly preferred surfactants are of the formula R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
Zur Gruppe dieser nichtionischen Tenside zƤhlen beispielsweise die C2-26 Fettalkohol-(PO)1-(EO)15-40-2-hydroxyalkylether, insbesondere auch die C8-10 Fettalkohol-(PO)1-(EO)22-2-hydroxydecylether.The group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
Besonders bevorzugt werden weiterhin solche endgruppenverschlossene poly(oxyalkylierten) Niotenside der Formel R1O[CH2CH2O]x[CH2CH(R3)O]yCH2CH(OH)R2, in der R1 und R2 unabhƤngig voneinander fĆ¼r einen linearen oder verzweigten, gesƤttigten oder ein- bzw. mehrfach ungesƤttigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R3 unabhƤngig voneinander ausgewƤhlt ist aus -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, vorzugsweise jedoch fĆ¼r -CH3 steht, und x und y unabhƤngig voneinander fĆ¼r Werte zwischen 1 und 32 stehen, wobei Niotenside mit R3 = -CH3 und Werten fĆ¼r x von 15 bis 32 und y von 0,5 und 1,5 ganz besonders bevorzugt sind.Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 , in which R 1 and R 2 independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 , but preferably -CH 3 , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R 3 = -CH 3 and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.
Weitere bevorzugt einsetzbare Niotenside sind die endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2, in der R1 und R2 fĆ¼r lineare oder verzweigte, gesƤttigte oder ungesƤttigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R3 fĆ¼r H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x fĆ¼r Werte zwischen 1 und 30, k und j fĆ¼r Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert x ā„ 2 ist, kann jedes R3 in der oben stehenden Formel R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2 unterschiedlich sein. R1 und R2 sind vorzugsweise lineare oder verzweigte, gesƤttigte oder ungesƤttigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. FĆ¼r den Rest R3 sind H, -CH3 oder -CH2CH3 besonders bevorzugt. Besonders bevorzugte Werte fĆ¼r x liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ā„ 2, each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different. R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R 3 , H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
Wie vorstehend beschrieben, kann jedes R3 in der oben stehenden Formel unterschiedlich sein, falls x ā„ 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise fĆ¼r 3, kann der Rest R3 ausgewƤhlt werden, um Ethylenoxid- (R3 = H) oder Propylenoxid- (R3 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefĆ¼gt sein kƶnnen, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 fĆ¼r x ist hierbei beispielhaft gewƤhlt worden und kann durchaus grƶĆer sein, wobei die Variationsbreite mit steigenden x-Werten zunimmt und beispielsweise eine groĆe Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschlieĆt, oder umgekehrt.As described above, each R 3 in the above formula may be different if x ā„ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R 3 can be selected to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3 ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
Besonders bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der oben stehenden Formel weisen Werte von k = 1 und j = 1 auf, so dass sich die vorstehende Formel zu R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2 vereinfacht. In der letztgenannten Formel sind R1, R2 und R3 wie oben definiert und x steht fĆ¼r Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R1 und R2 9 bis 14 C-Atome aufweisen, R3 fĆ¼r H steht und x Werte von 6 bis 15 annimmt.Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH ) CH 2 OR 2 simplified. In the latter formula, R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
Als besonders wirkungsvoll haben sich schlieĆlich die nichtionischen Tenside der allgemeine Formel R1-CH(OH)CH2O-(AO)w-R2 erwiesen, in der
- R1 fĆ¼r einen geradkettigen oder verzweigten, gesƤttigten oder ein- bzw. mehrfach ungesƤttigten C6-24-Alkyl- oder -Alkenylrest steht;
- R2 fĆ¼r einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- A fĆ¼r einen Rest aus der Gruppe CH2CH2, CH2CH2CH2, CH2CH(CH3), vorzugsweise fĆ¼r CH2CH2 steht, und
- w fĆ¼r Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht Zur Gruppe dieser nichtionischen Tenside zƤhlen beispielsweise die C4-22 Fettalkohol-(EO)10-80-2-hydroxyalkylether, insbesondere auch die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)40-80-2-hydroxyalkylether.
- R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
- R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ), preferably CH 2 CH 2 , and
- w is from 1 to 120, preferably from 10 to 80, in particular from 20 to 40. The group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-C 4-22 hydroxydecylether and the fatty alcohol (EO) 40-80 2-hydroxyalkyl ether.
In verschiedenen AusfĆ¼hrungsformen der Erfindung kƶnnen anstelle der oben definierten endgruppenverschlossenen Hydroxymischether auch die entsprechenden nicht endgruppenverschlossenen Hydroxymischether eingesetzt werden. Diese kƶnnen den obigen Formeln genĆ¼gen, wobei R2 aber Wasserstoff ist und R1, R3, A, A', A", A''', w, x, y und z wie oben definiert sind.In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R 2 is hydrogen and R 1 , R 3 , A, A ', A ", A''', w, x, y and z are as defined above.
Bevorzugte flĆ¼ssige Reinigungsmittel sind dadurch gekennzeichnet, dass das Reinigungsmittel mindestens ein nichtionisches Tensid, vorzugsweise ein nichtionisches Tensid aus der Gruppe der Hydroxymischether, enthƤlt, wobei der Gewichtsanteil des nichtionischen Tensids am Gesamtgewicht des gesamten Reinigungsmittels vorzugsweise 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 8,0 Gew.-% und insbesondere 1,0 bis 4,0 Gew.-% betrƤgt.Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the total cleaning agent preferably 0.1 to 10 wt .-%, preferably 0.5 to 8.0 wt .-% and in particular 1.0 to 4.0 wt .-% is.
GemĆ¤Ć einer bevorzugten AusfĆ¼hrungsform sind solche Hydroxymischether in der ersten und/oder der zweiten flĆ¼ssigen Zubereitung enthalten. Sind weitere Zubereitung im Reinigungsmittel vorhanden, kƶnnen diese auch nichtionische Tenside, insbesondere alkoxylierte Fettalkohole und/oder Hydroxymischether enthalten. Es kann besonders bevorzugt sein, wenn die o.g. Hydroxymischether in der zweiten flĆ¼ssigen Zubereitung enthalten sind.According to a preferred embodiment, such hydroxy mixed ethers are contained in the first and / or the second liquid preparation. If further preparation is present in the cleaning agent, these may also contain nonionic surfactants, in particular alkoxylated fatty alcohols and / or hydroxy mixed ethers. It may be particularly preferred if the o.g. Hydroxymischether contained in the second liquid preparation.
GemĆ¤Ć einer bevorzugten AusfĆ¼hrungsform enthƤlt die erste flĆ¼ssige Zubereitung mindestens ein nichtionisches Tensid, bevorzugt ausgewƤhlt aus der Gruppe der alkoxylierten Alkohole, insbesondere der vorstehend genannten alkoxylierten Alkohole.According to a preferred embodiment, the first liquid preparation contains at least one nonionic surfactant, preferably selected from the group of the alkoxylated alcohols, in particular the abovementioned alkoxylated alcohols.
GemĆ¤Ć einer bevorzugten AusfĆ¼hrungsform enthƤlt die erste flĆ¼ssige Zubereitung zwischen 1 und 75 Gew.-%, vorzugsweise 5 bis 60 Gew.-%, noch bevorzugter 10 bis 50 Gew.-% (jeweils bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Zubereitung) mindestens eines nichtionischen Tensids. Sind mehrere nichtionische Tenside enthalten, bezieht sich die vorstehend genannte Menge auf die Summe aller Nichtionischen Tenside in der ersten flĆ¼ssigen Zubereitung.According to a preferred embodiment, the first liquid preparation contains between 1 and 75% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight (based in each case on the total weight of the first liquid preparation) of at least one nonionic surfactant. If several nonionic surfactants are included, the aforementioned amount refers to the sum of all nonionic surfactants in the first liquid preparation.
Bevorzugt ist es insbesondere, wenn die erste flĆ¼ssige Zubereitung 25 bis 50 Gew.-% Alkalimetallcarbonat, bevorzugt Natriumcarbonat, und 10 bis 50 Gew.-% nichtionisches Tensid ausgewƤhlt aus den alkoxylierten Alkoholen, insbesondere solchen alkoxylierten Alkoholen der vorstehend genannten allgemeinen Formel (I), enthƤlt (jeweils bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Zubereitung). Die hier angegebenen MengenverhƤltnisse beziehen sich auf die Summe aller nichtionischen Tenside ausgewƤhlt aus den alkoxylierten Alkoholen in der ersten flĆ¼ssigen Zubereitung.It is particularly preferred if the first liquid preparation contains 25 to 50% by weight of alkali metal carbonate, preferably sodium carbonate, and 10 to 50% by weight of nonionic surfactant selected from the alkoxylated alcohols, in particular those alkoxylated alcohols of the abovementioned general formula (I) , contains (in each case based on the total weight of the first liquid preparation). The quantitative ratios given here are based on the sum of all nonionic surfactants selected from the alkoxylated alcohols in the first liquid preparation.
GemĆ¤Ć einer besonders bevorzugten AusfĆ¼hrungsform enthƤlt die erste flĆ¼ssige Zubereitung als ein nichtionisches Tensid eine Komponente gemĆ¤Ć der folgenden Formel (I)
āāāāāāāāR1-O-(CH2-CH(R2)-)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6
- wobei R1 ausgewƤhlt ist aus geradkettigen oder verzweigten, gesƤttigten C8-16-Alkylresten;
- R2 und R4 gleich -H, R3 und R5 gleich -CH3 sind,
- R6 ausgewƤhlt ist aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, -CH2CH(CH3)2, -C(CH3)3, C5-20-Alkyl (linear oder verzweigt),
- und unabhƤngig voneinander ausgewƤhlt sind
- w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- x = 0 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- y = 0 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
- z = 0 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3.
R 1 is -O- (CH 2 -CH (R 2 ) -) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 - CH (R 5 ) -O) z -R 6
- wherein R 1 is selected from straight-chain or branched, saturated C 8-16 -alkyl radicals;
- R 2 and R 4 are -H, R 3 and R 5 are -CH 3 ,
- R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -C (CH 3 ) 3 , C 5-20 alkyl (linear or branched),
- and are independently selected
- w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- x = 0 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- y = 0 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
- z = 0 to 6, preferably 1.5 to 4.5, in particular 2 to 3.
Diese vorstehend als bevorzugt ausgewƤhlten nichtionischen Tenside haben den Vorteil, dass sie in der Regel flĆ¼ssig bis pastƶs sind, und neben ihrer Wirkung als KlarspĆ¼ltensid, auch als flĆ¼ssige Matrixkomponente(n) in der ersten flĆ¼ssigen Zubereitung dienen kƶnnen.These nonionic surfactants selected above as preferred have the advantage that they are generally liquid to pasty, and in addition to their action as rinse aid surfactant, they can also serve as liquid matrix component (s) in the first liquid preparation.
Bevorzugt ist es insbesondere, wenn die erste flĆ¼ssige Zubereitung 25 bis 50 Gew.-% Alkalimetallcarbonat, bevorzugt Natriumcarbonat, und 10 bis 50 Gew.-% mindestens eines der im vorangegangenen Absatz als besonders bevorzugt gemĆ¤Ć Formel (I) beschriebenen nichtionischen Tenside enthƤlt. Sind mehrere nichtionische Tenside der im vorstehenden Absatz als bevorzugt genannten Tenside enthalten, so beziehen sich die angegebenen Mengen jeweils auf die Gesamtmenge der unter die bevorzugte Formel fallenden nichtionischen Tenside. Besonders bevorzugt sind dabei insbesondere solche Kombinationen, welche zusƤtzlich 0,3 bis 5 Gew.-%, bevorzugt 0,6 bis 3 Gew.-% eines synthetischen Li-Na-Mg-Schichtsilikats umfassen.It is particularly preferred if the first liquid preparation contains 25 to 50% by weight of alkali metal carbonate, preferably sodium carbonate, and 10 to 50% by weight of at least one of the nonionic surfactants described in the preceding paragraph as being particularly preferred according to formula (I). If a plurality of nonionic surfactants contain the surfactants mentioned as preferred in the preceding paragraph, then the stated amounts relate in each case to the total amount of the nonionic surfactants falling under the preferred formula. Particular preference is given in particular to those combinations which additionally comprise from 0.3 to 5% by weight, preferably from 0.6 to 3% by weight, of a synthetic Li-Na-Mg phyllosilicate.
Die genannten, insbesondere die als bevorzugt genannten nichtionischen Tenside kƶnnen (auch zusƤtzlich) in der zweiten flĆ¼ssigen Zubereitung enthalten sein.The nonionic surfactants mentioned, in particular those mentioned as being preferred, may also be present (also in addition) in the second liquid preparation.
Nach einer weiteren bevorzugten AusfĆ¼hrungsform enthalten die flĆ¼ssigen Zubereitungen jeweils ein oder mehrere Lƶsungsmittel, bevorzugt organische Lƶsungsmittel.According to a further preferred embodiment, the liquid preparations each contain one or more solvents, preferably organic solvents.
GemĆ¤Ć einer weiteren AusfĆ¼hrungsform sind als Lƶsungsmittel beispielsweise 1,2 Propandiol, 1,3-Propandiol, 2-Methyl-1,3-propandiol, Dipropylenglykol, Diethylenglykol, Alkanolamine, Glycerin, und/oder Mischung davon geeignet.According to a further embodiment, suitable solvents are, for example, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycol, diethylene glycol, alkanolamines, glycerol, and / or mixtures thereof.
Alkanolamine, wie insbesondere Monoethanolamin und Triethanolamin, sind ebenfalls geeignet, allerdings ist es bevorzugt, diese nur in geringen Mengen, insbesondere bis etwa5 Gew.-%) einzusetzen, da ansonsten eine BeeintrƤchtigung der IntegritƤt der umhĆ¼llenden Verpackung (insbesondere bei PVA-haltigen Folien) auftreten kann.Alkanolamines, such as in particular monoethanolamine and triethanolamine, are likewise suitable, although it is preferred that these be present only in small amounts, in particular up to about 5% by weight. otherwise it may impair the integrity of the enveloping package (especially in PVA-containing films).
Als Lƶsungsmittel bevorzugt sind insbesondere 1,2 Propandiol, 1,3-Propandiol, 2-Methyl-1,3-propandiol, Dipropylenglykole (einzeln oder als Mischung), Glycerin, und/oder Mischung davon. Ganz besonders bevorzugt ist der erfindungsgemƤĆe Einsatz von 1,2-Propandiol, Glycerin oder einer Mischung von 1,2-Propandiol und Glycerin.Particularly preferred solvents are 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycols (individually or as a mixture), glycerol, and / or a mixture thereof. Very particular preference is given to the use according to the invention of 1,2-propanediol, glycerol or a mixture of 1,2-propanediol and glycerol.
GemĆ¤Ć einer anderen AusfĆ¼hrungsform sind Lƶsungsmittel geeignet, welche ausgewƤhlt sind aus nicht leicht flĆ¼chtigen organischen Lƶsungsmitteln. Nicht leicht flĆ¼chtige organische Lƶsungsmittel im Sinne der vorliegenden Erfindung weisen eine FlĆ¼chtigkeit (auch VolatilitƤt oder Verdunstungszahl genannt) von mindestens 10, und insbesondere Ć¼ber 35, auf. Die FlĆ¼chtigkeit wird dabei angegeben als VerhƤltnis des Dampfdrucks des betrachteten Stoffs zum Dampfdruck des leicht flĆ¼chtigen Bezugsstoffs Diethylether bei 20 Ā°C und einer relativen Luftfeuchtigkeit von 65 Ā± 5%.In another embodiment, solvents are suitable which are selected from non-volatile organic solvents. Non-volatile organic solvents for the purposes of the present invention have a volatility (also called volatility or evaporation number) of at least 10, and in particular more than 35, on. The volatility is given as the ratio of the vapor pressure of the substance under consideration to the vapor pressure of the volatile reference substance diethyl ether at 20 Ā° C and a relative humidity of 65 Ā± 5%.
Zu den bevorzugten organischen Lƶsungsmitteln mit einer FlĆ¼chtigkeit von mindestens 10 und insbesondere von Ć¼ber 35, zƤhlen mehrwertige Alkohole wie 2-Methyl-1,3-Propandiol, 1,3-Propandiol, 1,2-Propylenglykol und Glycerin. Insbesondere sind solche organischen Lƶsungsmittel, insbesondere mehrwertige Alkohole bevorzugt, welche eine FlĆ¼chtigkeit von mehr als 50 aufweisen.Preferred organic solvents having a volatility of at least 10, and especially greater than 35 include polyhydric alcohols such as 2-methyl-1,3-propanediol, 1,3-propanediol, 1,2-propylene glycol and glycerin. In particular, those organic solvents, in particular polyhydric alcohols, which have a volatility of more than 50 are preferred.
Insbesondere wird auf organische Lƶsungsmittel, welche eine FlĆ¼chtigkeit unter 10 haben, ganz verzichtet.In particular, organic solvents which have a volatility of less than 10 are completely dispensed with.
Als nicht leicht flĆ¼chtige Lƶsungsmittel bevorzugt sind insbesondere 1,2 Propandiol, 1,3-Propandiol, 2-Methyl-1,3-propandiol, Dipropylenglykole, Glycerin, und/oder Mischung davon. Ganz besonders bevorzugt ist der erfindungsgemƤĆe Einsatz von 1,2-Propandiol, Glycerin oder einer Mischung von 1,2-Propandiol und Glycerin.Particularly preferred non-volatile solvents are 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycols, glycerol, and / or a mixture thereof. Very particular preference is given to the use according to the invention of 1,2-propanediol, glycerol or a mixture of 1,2-propanediol and glycerol.
Bevorzugt werden beim Einsatz der genannten Lƶsungsmittel in der ersten flĆ¼ssigen Zubereitung zusƤtzlich 0,3 bis 5 Gew.-%, insbesondere 0,6 bis 3 Gew.-% an magnesiumhaltigen Schichtsilikat, insbesondere an Lithium-Magnesium-Natrium-Schichtsilikat eingesetzt.When using said solvents in the first liquid preparation, preference is additionally given to using from 0.3 to 5% by weight, in particular from 0.6 to 3% by weight, of magnesium-containing phyllosilicate, in particular lithium-magnesium-sodium phyllosilicate.
GemĆ¤Ć einer weiteren AusfĆ¼hrungsform liegt das VerhƤltnis des Wassergehalts der ersten und der zweiten flĆ¼ssigen Zubereitungen zueinander (jeweils angegeben in Gew.-%, bezogen auf die Menge des Wassers am Gesamtgewicht der jeweiligen flĆ¼ssigen Zubereitung) zwischen 5:1 und 1:5, bevorzugt 3:1 und 1:3, bevorzugt zwischen 2:1 und 1:2. Dies hat den Vorteil, dass zwischen den einzelnen flĆ¼ssigen Zubereitungen Ć¼ber die wasserlƶsliche Verpackung keine zu groĆen (insbesondere optisch auffƤlligen) Migrationen des Wasser und/oder der Lƶsungsmittel auftreten. Optisch auffƤllige Migrationen kƶnnen dazu fĆ¼hren, dass eine der Kammern sich weiter aufblƤht/mit mehr FlĆ¼ssigkeit gefĆ¼llt ist, wƤhrend die andere Kammer FlĆ¼ssigkeit verliert und dadurch schrumpft. Insbesondere das Schrumpfen fĆ¼hrt zu optisch unansehnlichen vorportionierten Reinigungsmitteln, die vom Endverbraucher nicht akzeptiert werden.According to a further embodiment, the ratio of the water content of the first and the second liquid preparations to one another (in each case given in% by weight, based on the amount of water in the total weight of the respective liquid preparation) is between 5: 1 and 1: 5, preferably 3 : 1 and 1: 3, preferably between 2: 1 and 1: 2. This has the advantage that no too large (in particular optically conspicuous) migrations of the water and / or the solvents occur between the individual liquid preparations via the water-soluble packaging. Visually conspicuous migrations can cause one of the chambers to continue to inflate more fluid is filled while the other chamber loses fluid and thereby shrinks. In particular, the shrinkage leads to visually unsightly pre-portioned cleaning agents that are not accepted by the end user.
Vorteilhafterweise kƶnnen neben den Alkalimetallcarbonaten, zusƤtzliche GerĆ¼ststoffe eingesetzt werden. Zu den zusƤtzlich einsetzbaren GerĆ¼ststoffen zƤhlen insbesondere die Zeolithe, Silikate, Hydrogencarbonate, organische Cobuilder und - wo keine ƶkologischen Vorurteile gegen ihren Einsatz bestehen - auch die Phosphate. Vorzugsweise sind die Mittel aber phosphatfrei.Advantageously, in addition to the alkali metal carbonates, additional builders can be used. The additional builders that can be used include, in particular, the zeolites, silicates, bicarbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates. Preferably, however, the agents are phosphate-free.
Vorzugsweise kƶnnen kristalline schichtfƶrmige Silikate der allgemeinen Formel NaMSixO2x+1Ā· y H2O eingesetzt werden, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, wobei besonders bevorzugte Werte fĆ¼r x 2, 3 oder 4 sind, und y fĆ¼r eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht. Die kristallinen schichtfƶrmigen Silikate der Formel NaMSixO2x+1 Ā· y H2O werden beispielsweise von der Firma Clariant GmbH (Deutschland) unter dem Handelsnamen Na-SKS vertrieben. Beispiele fĆ¼r diese Silikate sind Na-SKS-1 (Na2Si22O45 Ā· x H2O, Kenyait), Na-SKS-2 (Na2Si14O29 Ā· x H2O, Magadiit), Na-SKS-3 (Na2Si8O17 Ā· x H2O) oder Na-SKS-4(Na2Si4O9 Ā· x H2O, Makatit). FĆ¼r die Zwecke der vorliegenden Erfindung besonders geeignet sind kristalline Schichtsilikate der Formel NaMSixO2x+1 Ā· y H2O, in denen x fĆ¼r 2 steht. Insbesondere sind sowohl Ć- als auch Ī“-Natriumdisitikate Na2Si2O5 Ā· y H2O sowie weiterhin vor allem Na-SKS-5 (Ī±-Na2Si2O5), Na-SKS-7 (Ī²-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5 Ā· H2O), Na-SKS-10 (NaHSi2O5 Ā· 3 H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (Ī“-Na2Si2O5) bevorzugt.Preference is given to using crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, in which M represents sodium or hydrogen, x represents from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite). Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi x O 2x + 1 .yH 2 O, in which x is 2. In particular, both .beta.- and Ī“-Natriumdisitikate Na 2 Si 2 O 5 Ā· y H 2 O, and further in particular Na-SKS-5 (Ī±-Na 2 Si 2 O 5), Na-SKS-7 (Ī²-Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 Ā· H 2 O), Na-SKS-10 (NaHSi 2o5 Ā· 3 H 2 O, kanemite), Na-SKS-11 (t- Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (Ī“-Na 2 Si 2 O 5 ).
Maschinelle GeschirrspĆ¼lmittel enthalten vorzugsweise einen Gewichtsanteil des kristallinen schichtfƶrmigen Silikats der Formel NaMSixO2x+1 Ā· y H2O von 0,1 bis 20 Gew.-%, bevorzugt von 0,2 bis 15 Gew.-% und insbesondere von 0,4 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht dieser Mittel.Machine dishwashing detergents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0, 4 to 10 wt .-%, each based on the total weight of these agents.
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O:SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise lƶseverzƶgert sind und SekundƤrwascheigenschaften aufweisen. Die Lƶseverzƶgerung gegenĆ¼ber herkƶmmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch OberflƤchenbehandlung, Compoundierung, Kompaktierung/Verdichtung oder durch Ćbertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" verstanden, dass die Silikate bei Rƶntgenbeugungsexperimenten keine scharfen Rƶntgenreflexe liefern, wie sie fĆ¼r kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Rƶntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen, hervorrufen.It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.
Im Rahmen der vorliegenden Erfindung ist es bevorzugt, dass diese(s) Silikat(e), vorzugsweise Alkalisilikate, besonders bevorzugt kristalline oder amorphe Alkalidisilikate, in den Mitteln in Mengen von 3 bis 60 Gew.-%, vorzugsweise von 8 bis 50 Gew.-% und insbesondere von 20 bis 40 Gew.-%, jeweils bezogen auf das Gewicht des maschinellen GeschirrspĆ¼lmittels, enthalten sind.In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt. % and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent are included.
SelbstverstƤndlich ist auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen mƶglich, sofern ein derartiger Einsatz nicht aus ƶkologischen GrĆ¼nden vermieden werden sollte. Unter der Vielzahl der kommerziell erhƤltlichen Phosphate haben die Alkalimetallphosphate unter besonderer Bevorzugung von Pentanatrium- oder Pentakaliumtriphosphat (Natrium- oder Kaliumtripolyphosphat) in der Reinigungsmittel-Industrie die grƶĆte Bedeutung.Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the detergent industry have the greatest importance.
Alkalimetallphosphate ist dabei die summarische Bezeichnung fĆ¼r die Alkalimetall- (insbesondere Natrium- und Kalium-) Salze der verschiedenen PhosphorsƤuren, bei denen man MetaphosphorsƤuren (HPO3)n und OrthophosphorsƤure H3PO4 neben hƶhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als AlkalitrƤger, verhindern KalkbelƤge auf Maschinenteilen bzw. Kalkinkrustationen auf Geschirrteilen und tragen Ć¼berdies zur Reinigungsleistung bei.Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations on crockery and also contribute to the cleaning performance.
Technisch besonders wichtige Phosphate sind das Pentanatriumtriphosphat, Na5P3O10 (Natriumtripolyphosphat) sowie das entsprechende Kaliumsalz Pentakaliumtriphosphat, K5P3O10 (Kaliumtripolyphosphat) und entsprechende Mischsalze (Natriumkaliumtripolyphosphate). Vorzugsweise sind die Mittel aber phosphatfrei.Technically particularly important phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate) and corresponding mixed salts (Natriumkaliumtripolyphosphate). Preferably, however, the agents are phosphate-free.
Werden im Rahmen der vorliegenden Anmeldung Phosphate als wasch- oder reinigungsaktive Substanzen im maschinellen GeschirrspĆ¼lmittel eingesetzt, so enthalten bevorzugte Mittel diese(s) Phosphat(e), vorzugsweise Alkalimetallphosphat(e), besonders bevorzugt Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat), in Mengen von 5 bis 80 Gew.-%, vorzugsweise von 10 bis 75 Gew.-% und insbesondere von 12,5 bis 70 Gew.-%, jeweils bezogen auf das Gewicht des gesamten maschinellen GeschirrspĆ¼lmittels.If phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application, preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 5 to 80 wt .-%, preferably from 10 to 75 wt .-% and in particular from 12.5 to 70 wt .-%, each based on the weight of the total automatic dishwashing detergent.
Alkalimetallhydrogencarbonate, Alkalimetallsesquicarbonate, die genannten Alkalisilikate, Alkalimetasilikate, und Mischungen der vorgenannten Stoffe kƶnnen ebenfalls zusƤtzlich zu den erfindungsgemƤĆen Alkalimetallcarbonaten eingesetzt werden, wobei im Sinne dieser Erfindung bevorzugt die Alkalihydrogencarbonate - und/oder -sequicarbonate, bevorzugt Natriumhydrogencarbonat oder Natriumsesquicarbonat eingesetzt werden kƶnnen.Alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances can likewise be used in addition to the alkali metal carbonates according to the invention, preference being given for the purposes of this invention to the use of the alkali hydrogencarbonates and / or -sequicarbonates, preferably sodium bicarbonate or sodium sesquicarbonate.
GemĆ¤Ć einer weiteren AusfĆ¼hrungsform ist ein Buildersystem, enthaltend eine Mischung aus Tripolyphosphat und Natriumcarbonat, bevorzugt. Aufgrund ihrer im Vergleich mit anderen Buildersubstanzen geringen chemischen KompatibilitƤt mit den Ć¼brigen Inhaltsstoffen von maschinellen GeschirrspĆ¼lmitteln, werden die optionalen Alkalimetallhydroxide bevorzugt nur in geringen Mengen, vorzugsweise in Mengen unterhalb 10 Gew.-%, bevorzugt unterhalb 6 Gew.-%, besonders bevorzugt unterhalb 4 Gew.-% und insbesondere unterhalb 2 Gew.-%, jeweils bezogen auf das Gesamtgewicht des maschinellen GeschirrspĆ¼lmittels, eingesetzt. Besonders bevorzugt werden Mittel, welche bezogen auf ihr Gesamtgewicht weniger als 0,5 Gew.-% und insbesondere keine Alkalimetallhydroxide enthalten.In another embodiment, a builder system containing a mixture of tripolyphosphate and sodium carbonate is preferred. Because of their low chemical compatibility with the other ingredients of dishwasher detergents in comparison with other builders, the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
Alternativ oder zusƤtzlich zu den Phosphaten, insbesondere den Polyphosphaten, kƶnnen auch andere GerĆ¼ststoffe, wie beispielsweise Zeolithe, Silikate, weiterhin auch insbesondere die Natriumhydrogencarbonat oder Natriumsesquicarbonat, und organische Cobuilder eingesetzt werden. Bevorzugt ist das Mittel frei von wasserunlƶslichen GerĆ¼ststoffen und enthƤlt insbesondere bevorzugt keine Zeolithe.As an alternative or in addition to the phosphates, in particular the polyphosphates, it is also possible to use other builders, such as, for example, zeolites, silicates, and in particular also the sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders. The agent is preferably free of water-insoluble builders and particularly preferably contains no zeolites.
Als Silikate kommen insbesondere kristalline schichtfƶrmige Silikate der allgemeinen Formel NaMSixO2x+1 y H2O, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, wobei besonders bevorzugte Werte fĆ¼r x 2, 3 oder 4 sind, und y fĆ¼r eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht, in Betracht. Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise lƶseverzƶgert sind und SekundƤrwascheigenschaften aufweisen.Particularly suitable silicates are crystalline layered silicates of the general formula NaMSi x O 2 Ć + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into account. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
GemĆ¤Ć einer bevorzugten AusfĆ¼hrungsform enthƤlt eine der flĆ¼ssigen Zubereitungen, bevorzugt zumindest die zweite flĆ¼ssige Zubereitung, beispielsweise die erste und die zweite flĆ¼ssige Zubereitung (sowie ggf. noch weitere im Reinigungsmittel vorhandene Zubereitungen) ferner mindestens einen Builder oder Co-Builder, insbesondere ausgewƤhlt aus der Gruppe gebildet aus Citrat, Aminocarboxylaten (insbesondere MGDA und/oder GLDA), Polyphosphaten (vorzugsweise einem Tripolyphosphat) sowie Phosphonaten und Mischungen davon. Insbesondere bevorzugt sind fĆ¼r phosphatfreie Reinigungsmittel die Builder oder Co-Builder ausgewƤhlt aus der Gruppe gebildet aus Citrat, Aminocarboxylaten (insbesondere MGDA und/oder GLDA) sowie Phosphonaten und Mischungen davon.According to a preferred embodiment, one of the liquid preparations, preferably at least the second liquid preparation, for example the first and the second liquid preparation (and optionally further preparations present in the cleaning agent) further contains at least one builder or co-builder, in particular selected from the group formed from citrate, aminocarboxylates (especially MGDA and / or GLDA), polyphosphates (preferably a tripolyphosphate) as well as phosphonates and mixtures thereof. Especially preferred for phosphate-free detergents are the builders or co-builders selected from the group formed from citrate, aminocarboxylates (in particular MGDA and / or GLDA) as well as phosphonates and mixtures thereof.
Als organische Cobuilder sind insbesondere Polycarboxylate / PolycarbonsƤuren, polymere Polycarboxylate, AsparaginsƤure, Polyacetale, Dextrine, weitere organische Cobuilder sowie Phosphonate zu nennen. Diese Stoffklassen werden nachfolgend beschrieben.Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
Brauchbare organische GerĆ¼stsubstanzen sind beispielsweise die in Form der freien SƤure und/oder ihrer Natriumsalze einsetzbaren PolycarbonsƤuren, wobei unter PolycarbonsƤuren solche CarbonsƤuren verstanden werden, die mehr als eine SƤurefunktion tragen. Beispielsweise sind dies CitronensƤure, AdipinsƤure, BernsteinsƤure, GlutarsƤure, ĆpfelsƤure, WeinsƤure, MaleinsƤure, FumarsƤure, ZuckersƤuren, NitrilotriessigsƤure (NTA), sofern ein derartiger Einsatz aus ƶkologischen GrĆ¼nden nicht zu beanstanden ist, sowie Mischungen aus diesen. Die freien SƤuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer SƤuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes der maschinellen GeschirrspĆ¼lmittel. Insbesondere sind hierbei CitronensƤure, BernsteinsƤure, GlutarsƤure, AdipinsƤure, GluconsƤure und beliebige Mischungen aus diesen zu nennen.Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
Eine weitere bedeutende Klasse der GerĆ¼ststoffe stellen AminocarbonsƤuren und/oder ihre Salze dar. Besonders bevorzugte Vertreter dieser Klasse sind MethylglycindiessigsƤure (MGDA) oder ihre Salze sowie GlutamindiessigsƤure (GLDA) oder ihre Salze oder EthylendiamindiessigsƤure oder ihre Salze (EDDS). Ebenfalls geeignet sind IminodibernsteinsƤure (IDS) und IminodiessigsƤure (IDA). AminocarbonsƤuren und ihre Salze kƶnnen zusammen mit den vorgenannten GerĆ¼ststoffen, insbesondere auch mit den phosphatfreien GerĆ¼ststoffen eingesetzt werden.Another important class of builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
Als GerĆ¼ststoffe sind weiter polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der PolyacrylsƤure oder der PolymethacrylsƤure, beispielsweise solche mit einer relativen MolekĆ¼lmasse von 500 bis 70000 g/mol.Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine MolekĆ¼lmasse von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer Ć¼berlegenen Lƶslichkeit kƶnnen aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein.Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der AcrylsƤure mit MethacrylsƤure und der AcrylsƤure oder MethacrylsƤure mit MaleinsƤure. Als besonders geeignet haben sich Copolymere der AcrylsƤure mit MaleinsƤure erwiesen, die 50 bis 90 Gew.-% AcrylsƤure und 50 bis 10 Gew.-% MaleinsƤure enthalten. Ihre relative MolekĆ¼lmasse, bezogen auf freie SƤuren, betrƤgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol.Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
Die Reinigungsmittel kƶnnen als GerĆ¼ststoff insbesondere auch Phosphonate enthalten. Als Phosphonat-Verbindung wird vorzugsweise ein Hydroxyalkan- und/oder Aminoalkanphosphonat eingesetzt. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren hƶhere Homologe in Frage. Phosphonate sind in den Mitteln vorzugsweise in Mengen von 0,1 bis 10 Gew.-%, insbesondere in Mengen von 0,5 bis 8 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Reinigungsmittels, enthalten.The detergents may contain, in particular, phosphonates as builder. As the phosphonate compound is preferably a hydroxyalkane and / or aminoalkane phosphonate used. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
Falls die erfindungsgemƤĆen Reinigungsmittel Phosphate, insbesondere Tripolyphosphate, enthalten, ist es bevorzugt, dass sie als weiteren Bestandteil vorzugsweise einen oder mehrere GerĆ¼ststoff(e) (Builder/Cobuilder) zusƤtzlich zu der phosphathaltigen Builderkomponente enthalten. Der Gewichtsanteil dieser zusƤtzlichen von der phosphathaltigen Builderkomponente verschiedenen GerĆ¼ststoffe am Gesamtgewicht der erfindungsgemƤĆen Mittel betrƤgt vorzugsweise 0,1 bis 10 Gew.-% und insbesondere 2 bis 7 Gew.-%. Zu diesen von der phosphathaltigen Builderkomponente verschiedenen GerĆ¼ststoffen zƤhlen insbesondere die oben als weitere GerĆ¼ststoffe beschriebenen, vorzugsweise Citrate, Phosphonate, MGDA, GLDA, IminodibernsteinsƤure, IminodiessigsƤure, EDDS (Ethylendiamin-N,N'-dibernsteinsƤure) oder die Salze der genannten SƤuren, andere organische Cobuilder und Silikate.If the cleaning agents according to the invention contain phosphates, in particular tripolyphosphates, it is preferred that they contain as further constituent preferably one or more builder (s) (builder / cobuilder) in addition to the phosphate-containing builder component. The proportion by weight of these additional builders differing from the phosphate-containing builder component in the total weight of the compositions according to the invention is preferably from 0.1 to 10% by weight and in particular from 2 to 7% by weight. These builders other than the phosphate-containing builder component include in particular those described above as further builders, preferably citrates, phosphonates, MGDA, GLDA, iminodisuccinic acid, iminodiacetic acid, EDDS (ethylenediamine-N, N'-disuccinic acid) or the salts of said acids, other organic Cobuilders and silicates.
Besonders bevorzugte phosphathaltige Reinigungsmittel enthalten als einen ihrer wesentlichen von der phosphathaltigen Builderkomponente unterschiedlichen GerĆ¼ststoffe Citrat, beispielsweise Natrium- oder Kaliumcitrat. Reinigungsmittel, die 1 bis 10 Gew.-%, vorzugsweise 2 bis 5 Gew.-% Citrat enthalten, sind erfindungsgemĆ¤Ć bevorzugt. ZusƤtzlich oder alternativ kƶnnen besonders bevorzugte phosphathaltige Reinigungsmittel als einen von der phosphathaltigen Builderkomponente unterschiedlichen GerĆ¼ststoff Phosphonate, beispielsweise HEDP, enthalten. Reinigungsmittel, die 1 bis 10 Gew.-%, vorzugsweise 2 bis 5 Gew.-% Phosphonat, insbesondere HEDP, enthalten, sind erfindungsgemĆ¤Ć bevorzugt.Particularly preferred phosphate-containing detergents contain citrate, for example sodium or potassium citrate, as one of their essential builders other than the phosphate-containing builder component. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of citrate are preferred according to the invention. Additionally or alternatively, particularly preferred phosphate-containing detergents may contain phosphonates, such as HEDP, as a builder other than the phosphate-containing builder component. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of phosphonate, in particular HEDP, are preferred according to the invention.
Die erfindungsgemƤĆen Reinigungsmittel kƶnnen ferner ein Sulfopolymer enthalten. Bevorzugt ist das Sulfopolymer in der zweiten flĆ¼ssigen Phase enthalten. Der Gewichtsanteil des Sulfopolymers am Gesamtgewicht des erfindungsgemƤĆen Reinigungsmittels betrƤgt vorzugsweise von 0,1 bis 20 Gew.-%, insbesondere von 0,5 bis 18 Gew.-%, besonders bevorzugt 1,0 bis 15 Gew.-%, insbesondere von 2 bis 14 Gew.-%, vor allem von 3 bis 12 Gew.-%, ganz besonders von 4 bis 8 Gew.-% . Das Sulfopolymer wird Ć¼blicherweise in Form einer wƤssrigen Lƶsung eingesetzt, wobei die wƤssrigen Lƶsungen typischerweise 20 bis 70 Gew.-%, insbesondere 30 bis 50 Gew.-%, vorzugsweise etwa 35 bis 40 Gew.-% Sulfopolymer(e) enthalten. Bei wasserarmen Zubereitungen kƶnnen die Sulfopolymere auch als Feststoffe, beispielsweise als Granulate eingesetzt werden.The cleaning agents of the invention may further contain a sulfopolymer. Preferably, the sulfopolymer is contained in the second liquid phase. The proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 2 to 14 wt .-%, especially from 3 to 12 wt .-%, especially from 4 to 8 wt .-%. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymer (s). For low-water preparations, the sulfopolymers can also be used as solids, for example as granules.
Als Sulfopolymer wird vorzugsweise ein copolymeres Polysulfonat, vorzugsweise ein hydrophob modifiziertes copolymeres Polysulfonat, eingesetzt.The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
Die Copolymere kƶnnen zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen.The copolymers may have two, three, four or more different monomer units.
Bevorzugte copolymere Polysulfonate enthalten neben SulfonsƤuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesƤttigten CarbonsƤuren.Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
Als ungesƤttigte CarbonsƤure(n) wird/werden mit besonderem Vorzug ungesƤttigte CarbonsƤuren der Formel R1(R2)C=C(R3)COOH eingesetzt, in der R1 bis R3 unabhƤngig voneinander fĆ¼r -H, -CH3, einen geradkettigen oder verzweigten gesƤttigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesƤttigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder fĆ¼r -COOH oder -COOR4 steht, wobei R4 ein gesƤttigter oder ungesƤttigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.Unsaturated carboxylic acid (s) used are, with particular preference, unsaturated carboxylic acids of the formula R 1 (R 2 ) C =C (R 3 ) COOH, in which R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH 2 , -OH or -COOH as defined above or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
Besonders bevorzugte ungesƤttigte CarbonsƤuren sind AcrylsƤure, MethacrylsƤure, EthacrylsƤure, Ī±-ChloroacrylsƤure, Ī±-CyanoacrylsƤure, CrotonsƤure, Ī±-Phenyl-AcrylsƤure, MaleinsƤure, MaleinsƤureanhydrid, FumarsƤure, ItaconsƤure, CitraconsƤure, MethylenmalonsƤure, SorbinsƤure, ZimtsƤure oder deren Mischungen. Einsetzbar sind selbstverstƤndlich auch die ungesƤttigten DicarbonsƤuren.Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, Ī±-chloroacrylic acid, Ī±-cyanoacrylic acid, crotonic acid, Ī±-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
Bei den SulfonsƤuregruppen-haltigen Monomeren sind solche der Formel
āāāāāāāāR5(R6)C=C(R7)-X-SO3H
bevorzugt, in der R5 bis R7 unabhƤngig voneinander fĆ¼r -H, -CH3, einen geradkettigen oder verzweigten gesƤttigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesƤttigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit - NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder fĆ¼r -COOH oder -COOR4 steht, wobei R4 ein gesƤttigter oder ungesƤttigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X fĆ¼r eine optional vorhandene Spacergruppe steht, die ausgewƤhlt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.In the sulfonic acid-containing monomers are those of the formula
R 5 (R 6 ) C = C (R 7 ) -X-SO 3 H
in which R 5 to R 7 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 - , -C (O) -NH-C (CH 3 ) 2 -CH 2 - and -C (O) -NH-CH (CH 3 ) -CH 2 -.
Unter diesen Monomeren bevorzugt sind solche der Formeln
āāāāāāāāH2C=CH-X-SO3H
āāāāāāāāH2C=C(CH3)-X-SO3H
āāāāāāāāHO3S-X-(R6)C=C(R7)-X-SO3H,
Preferred among these monomers are those of the formulas
H 2 C = CH-X-SO 3 H
H 2 C = C (CH 3 ) -X-SO 3 H
HO 3 SX- (R 6 ) C = C (R 7 ) -X-SO 3 H,
in denen R6 und R7 unabhƤngig voneinander ausgewƤhlt sind
aus -H, -CH3, -CH2CH3, -CH2CH2CH3 und -CH(CH3)2 und X fĆ¼r eine optional vorhandene Spacergruppe steht, die ausgewƤhlt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.in which R 6 and R 7 are independently selected
from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 and -CH (CH 3 ) 2 and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 -, -C (O) -NH-C (CH 3 ) 2 -CH 2 - and -C (O) -NH-CH (CH 3 ) -CH 2 -.
Besonders bevorzugte SulfonsƤuregruppen-haltige Monomere sind dabei 1-Acrylamido-1-propansulfonsƤure, 2-Acrylamido-2-propansulfonsƤure, 2-Acrylamido-2-methyl-1-propansulfonsƤure, 2-Methacrylamido-2-methyl-1-propansulfonsƤure, 3-Methacrylamido-2-hydroxy-propansulfonsƤure, AllylsulfonsƤure, MethallylsulfonsƤure, AllyloxybenzolsulfonsƤure, MethallyloxybenzolsulfonsƤure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsƤure, 2-Methyl-2-propen1-sulfonsƤure, StyrolsulfonsƤure, VinylsulfonsƤure, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten SƤuren oder deren wasserlƶsliche Salze.Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.
In den Polymeren kƶnnen die SulfonsƤuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. dass das acide Wasserstoffatom der SulfonsƤuregruppe in einigen oder allen SulfonsƤuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten SulfonsƤuregruppen-haltigen Copolymeren ist erfindungsgemĆ¤Ć bevorzugt.In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
Die Monomerenverteilung der erfindungsgemĆ¤Ć bevorzugt eingesetzten Copolymere betrƤgt bei Copolymeren, die nur CarbonsƤuregruppen-haltige Monomere und SulfonsƤuregruppen-haltige Monomere enthalten, vorzugsweise jeweils 5 bis 95 Gew.-%, besonders bevorzugt betrƤgt der Anteil des SulfonsƤuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des CarbonsƤuregruppen-haltigen Monomers 10 bis 50 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewƤhlt aus den zuvor genannten.The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
Die Molmasse der erfindungsgemĆ¤Ć bevorzugt eingesetzten Sulfo-Copolymere kann variiert werden, um die Eigenschaften der Polymere dem gewĆ¼nschten Verwendungszweck anzupassen. Bevorzugte Reinigungsmittel sind dadurch gekennzeichnet, dass die Copolymere Molmassen von 2000 bis 200.000 gmol-1, vorzugsweise von 4000 bis 25.000 gmol-1 und insbesondere von 5000 bis 15.000 gmol-1 aufweisen.The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
In einer weiteren bevorzugten AusfĆ¼hrungsform umfassen die Copolymere neben Carboxylgruppen-haltigem Monomer und SulfonsƤuregruppen-haltigem Monomer weiterhin wenigstens ein nichtionisches, vorzugsweise hydrophobes Monomer. Durch den Einsatz dieser hydrophob modifizierten Polymere konnte insbesondere die Leistung, insbesondere die KlarspĆ¼lleistung erfindungsgemƤĆer maschineller GeschirrspĆ¼lmittel verbessert werden.In a further preferred embodiment, in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. Through the use of these hydrophobically modified polymers, it was possible in particular to improve the performance, in particular the rinsing performance of automatic dishwasher detergents according to the invention.
Anionische Copolymere umfassend CarbonsƤuregruppen-haltige Monomere, SulfonsƤuregruppen-haltige Monomere und nichtionische Monomere, insbesondere hydrophobe Monomere, werden daher erfindungsgemĆ¤Ć bevorzugt.Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
Als nichtionische Monomere werden vorzugsweise Monomere der allgemeinen Formel R1(R2)C=C(R3)-X-R4 eingesetzt, in der R1 bis R3 unabhƤngig voneinander fĆ¼r -H, -CH3 oder -C2H5 steht, X fĆ¼r eine optional vorhandene Spacergruppe steht, die ausgewƤhlt ist aus -CH2-, -C(O)O- und -C(O)-NH-, und R4 fĆ¼r einen geradkettigen oder verzweigten gesƤttigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder fĆ¼r einen ungesƤttigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht.The nonionic monomers used are preferably monomers of the general formula R 1 (R 2 ) C =C (R 3 ) -XR 4 , in which R 1 to R 3 independently of one another are -H, -CH 3 or -C 2 H 5 , X represents an optionally present spacer group selected from -CH 2 -, -C (O) O- and -C (O) -NH-, and R 4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
Besonders bevorzugte nichtionische Monomere sind Buten, Isobuten, Penten, 3-Methylbuten, 2-Methylbuten, Cyclopenten, Hexen, Hexen-1, 2-Methlypenten-1, 3-Methlypenten-1, Cyclohexen, Methylcyclopenten, Cyclohepten, Methylcyclohexen, 2,4,4-Trimethylpenten-1, 2,4,4-Trimethylpenten-2, 2,3-Dimethylhexen-1, 2,4-Diemthylhexen-1, 2,5-Dimethlyhexen-1, 3,5-Dimethylhexen-1, 4,4-Dimehtylhexan-1, Ethylcyclohexyn, 1-Octen, Ī±-Olefine mit 10 oder mehr Kohlenstoffatomen wie beispielsweise 1-Decen, 1-Dodecen, 1-Hexadecen, 1-Oktadecen und C22-Ī±-Olefin, 2-Styrol, Ī±-Methylstyrol, 3-Methylstyrol, 4-Propylstryol, 4-Cyclohexylstyrol, 4-Dodecylstyrol, 2-Ethyl-4-Benzylstyrol, 1-Vinylnaphthalin, 2,Vinylnaphthalin, AcrylsƤuremethylester, AcrylsƤureethylester, AcrylsƤurepropylester, AcrylsƤurebutylester, AcrylsƤurepentylester, AcrylsƤurehexylester, MethacrylsƤuremethylester, N-(Methyl)acrylamid, AcrylsƤure-2-Ethylhexylester, MethacrylsƤure-2-Ethylhexylester, N-(2-Ethylhexyl)acrylamid, AcrylsƤureoctylester, MethacrylsƤureoctylester, N-(Octyl)acrylamid, AcrylsƤurelaurylester, MethacrylsƤurelaurylester, N-(Lauryl)acrylamid, AcrylsƤurestearylester, MethacrylsƤurestearylester, N-(Stearyl)acrylamid, AcrylsƤurebehenylester, MethacrylsƤurebehenylester und N-(Behenyl)acrylamid oder deren Mischungen.Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, Ī±-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-Ī±-olefin, 2-styrene, Ī± Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, AcrylsƤurectctyle ster, MethacrylsƤureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, and MethacrylsƤurebehenylester N- (Behenyl) acrylamide or mixtures thereof.
Die Monomerenverteilung der erfindungsgemĆ¤Ć bevorzugt eingesetzten hydrophob modifizierten Copolymere betrƤgt in Bezug auf das SulfonsƤuregruppen-haltige Monomer, das hydrophobe Monomer und das CarbonsƤuregruppen-haltige Monomer vorzugsweise jeweils 5 bis 80 Gew.-%, besonders bevorzugt betrƤgt der Anteil des SulfonsƤuregruppen-haltigen Monomers und des hydrophoben Monomers jeweils 5 bis 30 Gew.-% und der Anteil des CarbonsƤuregruppen-haltigenThe monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing
Monomers 60 bis 80 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewƤhlt aus den zuvor genannten.Monomers 60 to 80 wt .-%, the monomers are hereby preferably selected from the aforementioned.
In ErgƤnzung zu den vorgenannten von der phosphathaltigen Builderkomponente verschiedenen GerĆ¼ststoffen kƶnnen die Reinigungsmittel Alkalimetallhydroxide enthalten. Diese AlkalitrƤger werden in den Reinigungsmitteln bevorzugt nur in geringen Mengen, vorzugsweise in Mengen unterhalb 10 Gew.-%, bevorzugt unterhalb 6 Gew.-%, vorzugsweise unterhalb 5 Gew.-%, besonders bevorzugt zwischen 0,1 und 5 Gew.-% und insbesondere zwischen 0,5 und 5 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Reinigungsmittels eingesetzt. Alternative erfindungsgemƤĆe Reinigungsmittel sind frei von Alkalimetallhydroxiden.In addition to the aforementioned builders other than the phosphate-containing builder component, the detergents may contain alkali metal hydroxides. These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used. Alternative cleaning agents according to the invention are free of alkali metal hydroxides.
Die erfindungsgemƤĆen Mittel enthalten vorzugsweise mindestens einen weiteren Bestandteil, vorzugsweise ausgewƤhlt aus der Gruppe bestehend aus anionischen, kationischen und amphoteren Tensiden, Bleichmitteln, Bleichaktivatoren, Bleichkatalysatoren, Enzymen, Verdickern, Sequestrierungsmitteln, Elektrolyten, Korrosionsinhibitoren, insbesondere Silberschutzmitteln, Glaskorrosionsinhibitoren, Schauminhibitoren, Farbstoffen, Duftstoffen, Bitterstoffen, und antimikrobiellen Wirkstoffen.The agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances, and antimicrobial agents.
In der ersten flĆ¼ssigen Zubereitung kƶnnen insbesondere pH-Stellmittel (insbesondere Alkalimetallhydrogencarbonat (e)), Farbstoff(e), Duftstoffe und/oder Konservierungsmittel enthalten sein.In the first liquid preparation, in particular pH stabilizers (in particular alkali metal bicarbonate (s)), dye (s), fragrances and / or preservatives may be contained.
GemĆ¤Ć einer weiteren bevorzugten AusfĆ¼hrungsform enthƤlt bevorzugt eine der flĆ¼ssigen Zubereitungen, bevorzugt die zweite flĆ¼ssige Zubereitung, einen oder mehrere der Stoffe ausgewƤhlt aus der Gruppe bestehend aus pH-Stellmitteln, anionischen, kationischen und amphoteren Tensiden, Bleichaktivatoren, Bleichkatalysatoren, Enzymen, Verdickern, Sequestrierungsmitteln, Elektrolyten, Korrosionsinhibitoren, insbesondere Silberschutzmitteln, Glaskorrosionsinhibitoren, Schauminhibitoren, Duftstoffen, Bitterstoffen, und antimikrobiellen Wirkstoffen.According to a further preferred embodiment, one of the liquid preparations, preferably the second liquid preparation, preferably contains one or more substances selected from the group consisting of pH regulators, anionic, cationic and amphoteric surfactants, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, Electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, perfumes, bitter substances, and antimicrobial agents.
GemĆ¤Ć einer besonders bevorzugten AusfĆ¼hrungsform enthƤlt die zweite flĆ¼ssige Zubereitung, einen oder mehrere der Stoffe ausgewƤhlt aus der Gruppe bestehend aus pH-Stellmitteln, anionischen, kationischen und amphoteren Tensiden, Enzymen, Verdickern, Sequestrierungsmitteln, Elektrolyten, Korrosionsinhibitoren, insbesondere Silberschutzmitteln, Glaskorrosionsinhibitoren, Schauminhibitoren, Duftstoffen, Bitterstoffen, und antimikrobiellen Wirkstoffen.According to a particularly preferred embodiment, the second liquid preparation contains one or more substances selected from the group consisting of pH regulators, anionic, cationic and amphoteric surfactants, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, Fragrances, bitter substances, and antimicrobial agents.
Bevorzugt sind Farbstoffe mindestens in einer, bevorzugt in der ersten und der zweiten flĆ¼ssigen Zubereitung, insbesondere in allen Zubereitungen enthalten.Dyes are preferably present in at least one, preferably in the first and the second liquid preparation, in particular in all preparations.
Bevorzugte anionische Tenside sind Fettalkoholsulfate, Fettalkoholethersulfate, Dialkylethersulfate, Monoglyceridsulfate, Alkylbenzolsulfonate, Olefinsulfonate, Alkansulfonate, Ethersulfonate, n-Alkylethersulfonate, Estersulfonate und Ligninsulfonate. Ebenfalls im Rahmen der vorliegenden Erfindung verwendbar sind FettsƤurecyanamide, Sulfosuccinate (SulfobernsteinsƤureester), insbesondere SulfobernsteinsƤuremono- und -di-C8-C18-Alkylester, Sulfosuccinamate, Sulfosuccinamide, FettsƤureisethionate, Acylaminoalkansulfonate (FettsƤuretauride), FettsƤuresarcosinate, EthercarbonsƤuren und Alkyl(ether)phosphate sowie Ī±-SulfofettsƤuresalze, Acylglutamate, Monoglyceriddisulfate und Alkylether des Glycerindisulfats.Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and Ī±-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
Die anionischen Tenside werden vorzugsweise als Natriumsalze eingesetzt, kƶnnen aber auch als andere Alkali- oder Erdalkalimetallsalze, beispielsweise Kalium- oder Magnesiumsalze, sowie in Form von Ammonium- oder Mono-, Di-, Tri- bzw. Tetraalkylammoniumsalzen enthalten sein, im Falle der Sulfonate auch in Form ihrer korrespondierenden SƤure, z.B. DodecylbenzolsulfonsƤure.The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.
Geeignete Amphotenside sind beispielsweise Betaine der Formel (Riii)(Riv)(Rv)N+CH2COO-, in der Riii einen gegebenenfalls durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und Riv sowie Rv gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten, insbesondere C10-C18-Alkyl-dimethylcarboxymethylbetain und C11-C17-Alkylamidopropyl-dimethylcarboxymethylbetain.Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethylbetain and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethylbetain.
Geeignete Kationtenside sind u.a. die quartƤren Ammoniumverbindungen der Formel (Rvi)(Rvii)(Rviii)(Rix)N+ X-, in der Rvi bis Rix fĆ¼r vier gleich- oder verschiedenartige, insbesondere zwei lang- und zwei kurzkettige, Alkylreste und X- fĆ¼r ein Anion, insbesondere ein Halogenidion, stehen, beispielsweise Didecyl-dimethyl-ammoniumchlorid, Alkyl-benzyl-didecyl-ammoniumchlorid und deren Mischungen. Weitere geeignete kationische Tenside sind die quaternƤren oberflƤchenaktiven Verbindungen, insbesondere mit einer Sulfonium-, Phosphonium-, Jodonium- oder Arsoniumgruppe, die auch als antimikrobielle Wirkstoffe bekannt sind. Durch den Einsatz von quaternƤren oberflƤchenaktiven Verbindungen mit antimikrobieller Wirkung kann das Mittel mit einer antimikrobiellen Wirkung ausgestaltet werden bzw. dessen gegebenenfalls aufgrund anderer Inhaltsstoffe bereits vorhandene antimikrobielle Wirkung verbessert werden.Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix are four identical or different, in particular two long and two short-chain, alkyl radicals and X - are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
Als Glaskorrosionsinhibitoren werden beispielsweise Polyethylenimine oder Zinksalze, vorzugsweise Zinksalze, insbesondere Zinkacetat, eingesetzt. Glaskorrosionsinhibitoren sind in erfindungsgemƤĆen Mitteln vorzugsweise in einer Menge von 0,05 bis 5 Gew.-%, insbesondere in einer Menge von 0,1 bis 2 Gew.-%, enthalten.Examples of glass corrosion inhibitors used are polyethyleneimines or zinc salts, preferably zinc salts, in particular zinc acetate. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
Zu den Enzymen gehƶren insbesondere Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natĆ¼rlichen Ursprungs; ausgehend von den natĆ¼rlichen MolekĆ¼len stehen fĆ¼r den Einsatz in Reinigungsmitteln verbesserte Varianten zur VerfĆ¼gung, die entsprechend bevorzugt eingesetzt werden. ErfindungsgemƤĆe Reinigungsmittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret-Verfahren bestimmt werden.The enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly. Detergents according to the invention preferably contain enzymes in total amounts of from 1 Ć 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
Unter den Proteasen sind solche vom Subtilisin-Typ bevorzugt. Beispiele hierfĆ¼r sind die Subtilisine BPN' und Carlsberg sowie deren weiterentwickelte Formen, die Protease PB92, die Subtilisine 147 und 309, die Alkalische Protease aus Bacillus lentus, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7.Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
Beispiele fĆ¼r erfindungsgemĆ¤Ć einsetzbare Amylasen sind die Ī±-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens, aus B. stearothermophilus, aus Aspergillus niger und A. oryzae sowie die fĆ¼r den Einsatz in Reinigungsmitteln verbesserten Weiterentwicklungen der vorgenannten Amylasen. Desweiteren sind fĆ¼r diesen Zweck die Ī±-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. agaradherens (DSM 9948) hervorzuheben.Examples of amylases which can be used according to the invention are the Ī±-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the Ī±-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
ErfindungsgemĆ¤Ć einsetzbar sind weiterhin Lipasen oder Cutinasen, insbesondere wegen ihrer Triglycerid-spaltenden AktivitƤten, aber auch, um aus geeigneten Vorstufen in situ PersƤuren zu erzeugen. Hierzu gehƶren beispielsweise die ursprĆ¼nglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhƤltlichen, beziehungsweise weiterentwickelten Lipasen, insbesondere solche mit einem oder mehreren der folgenden AminosƤureaustausche ausgehend von der genannten Lipase in den Positionen D96L, T213R und/oder N233R, besonders bevorzugt alle der Austausche D96L, T213R und N233R.Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from, or further developed, Humicola lanuginosa (Thermomyces lanuginosus), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most preferably all of the exchanges D96L, T213R and N233R.
Weiterhin kƶnnen Enzyme eingesetzt werden, die unter dem Begriff Hemicellulasen zusammengefasst werden. Hierzu gehƶren beispielsweise Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Pektatlyasen, Xyloglucanasen (=Xylanasen), Pullulanasen und Ī²-Glucanasen.Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and Ī²-glucanases.
Zur Erhƶhung der bleichenden Wirkung kƶnnen erfindungsgemĆ¤Ć Oxidoreduktasen, beispielsweise Oxidasen, Oxygenasen, Katalasen, Peroxidasen, wie Halo-, Chloro-, Bromo-, Lignin-, Glucose- oder Mangan-peroxidasen, Dioxygenasen oder Laccasen (Phenoloxidasen, Polyphenoloxidasen) eingesetzt werden. Vorteilhafterweise werden zusƤtzlich vorzugsweise organische, besonders bevorzugt aromatische, mit den Enzymen wechselwirkende Verbindungen zugegeben, um die AktivitƤt der betreffenden Oxidoreduktasen zu verstƤrken (Enhancer) oder um bei stark unterschiedlichen Redoxpotentialen zwischen den oxidierenden Enzymen und den Anschmutzungen den Elektronenfluss zu gewƤhrleisten (Mediatoren).Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases), can be used according to the invention to increase the bleaching effect. be used. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
Ein Protein und/oder Enzym kann besonders wƤhrend der Lagerung gegen SchƤdigungen wie beispielsweise Inaktivierung, Denaturierung oder Zerfall etwa durch physikalische EinflĆ¼sse, Oxidation oder proteolytische Spaltung geschĆ¼tzt werden. Bei mikrobieller Gewinnung der Proteine und/oder Enzyme ist eine Inhibierung der Proteolyse besonders bevorzugt, insbesondere wenn auch die Mittel Proteasen enthalten. Reinigungsmittel kƶnnen zu diesem Zweck Stabilisatoren enthalten; die Bereitstellung derartiger Mittel stellt eine bevorzugte AusfĆ¼hrungsform der vorliegenden Erfindung dar.A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
Reinigungsaktive Proteasen und Amylasen werden in der Regel nicht in Form des reinen Proteins sondern vielmehr in Form stabilisierter, lager- und transportfƤhiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zƤhlen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen PrƤparationen oder, insbesondere bei flĆ¼ssigen oder gelfƶrmigen Mitteln, Lƶsungen der Enzyme, vorteilhafterweise mƶglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
Alternativ kƶnnen die Enzyme sowohl fĆ¼r die feste als auch fĆ¼r die flĆ¼ssige Darreichungsform verkapselt werden, beispielsweise durch SprĆ¼htrocknung oder Extrusion der Enzymlƶsung zusammen mit einem vorzugsweise natĆ¼rlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlƤssigen Schutzschicht Ć¼berzogen ist. In aufgelagerten Schichten kƶnnen zusƤtzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch SchĆ¼ttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
Weiterhin ist es mƶglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere EnzymaktivitƤten aufweist.Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.
Wie aus der vorherigen AusfĆ¼hrungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts Ć¼blicher Enzym-Zubereitungen. ErfindungsgemĆ¤Ć bevorzugt eingesetzte Protease- und Amylase-Zubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins.As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Preferably used according to the invention Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10 Wt .-% of the enzyme protein.
Bevorzugt werden insbesondere solche Reinigungsmittel, die, jeweils bezogen auf ihr Gesamtgewicht, 0,1 bis 12 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% Enzym-Zubereitungen enthalten.Particular preference is given to detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
GemĆ¤Ć einer besonders bevorzugten AusfĆ¼hrungsform ist die erste flĆ¼ssige Zubereitung im wesentlichen frei von Enzymen. Im wesentlichen frei von Enzymen bedeutet, dass die erste flĆ¼ssige Zubereitung, welche das Alkalimetallcarbonat, insbesondere das Natriumcarbonat, enthƤlt, weniger als 1 Gew.-%, insbesondere weniger als 0,1 Gew.-% Enzymzubereitung (bezogen auf das Gesamtgewicht der ersten flĆ¼ssigen Zubereitung) enthƤlt.According to a particularly preferred embodiment, the first liquid preparation is substantially free of enzymes. Substantially free of enzymes means that the first liquid preparation containing the alkali metal carbonate, especially the sodium carbonate, less than 1 wt .-%, in particular less than 0.1 wt .-% enzyme preparation (based on the total weight of the first liquid Preparation).
Bevorzugt werden die Enzyme, insbesondere die Amylase(n) und/oder Protease(n), in der zweiten flĆ¼ssigen Zubereitung eingesetzt.The enzymes, in particular the amylase (s) and / or protease (s), are preferably used in the second liquid preparation.
Generell kann der pH-Wert des Reinigungsmittels mittels Ć¼blicher pH-Regulatoren eingestellt werden, wobei der pH-Wert abhƤngig von dem gewĆ¼nschten Einsatzzweck gewƤhlt wird. In verschiedenen AusfĆ¼hrungsformen liegt der pH-Wert in einem Bereich von 5,5 bis 10,5, vorzugsweise 5,5 bis 9,5, noch bevorzugter 7 bis 9, insbesondere grƶĆer 7, vor allem im Bereich 7,5 bis 8,5. Als pH-Stellmittel dienen SƤuren und/oder Alkalien. Geeignete SƤuren sind insbesondere organische SƤuren wie die EssigsƤure, ZitronensƤure, GlycolsƤure, MilchsƤure, BernsteinsƤure, AdipinsƤure, ĆpfelsƤure, WeinsƤure und GluconsƤure oder auch AmidosulfonsƤure. Daneben kƶnnen aber auch die MineralsƤuren SalzsƤure, SchwefelsƤure und SalpetersƤure bzw. deren Mischungen eingesetzt werden. Geeignete Basen stammen aus der Gruppe der Alkali- und Erdalkalimetallhydroxide und -carbonate, insbesondere der Alkalimetallhydrogencarbonate, von denen Kaliumhydrogencarbonat und vor allem Natriumhydrogencarbonat bevorzugt ist.In general, the pH of the cleaning agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application. In various embodiments, the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5 , The pH-adjusting agents are acids and / or alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali metal hydroxides and alkaline earth metal hydroxides and carbonates, in particular the alkali metal bicarbonates, of which potassium bicarbonate and especially sodium bicarbonate is preferred.
Es kann ggf. auch flĆ¼chtiges Alkali, beispielsweise in Form von Ammoniak und/oder Alkanolaminen, die bis zu 9 C-Atome im MolekĆ¼l enthalten kƶnnen. Das Alkanolamin ist hierbei vorzugsweise ausgewƤhlt aus der Gruppe bestehend aus Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen. Das Alkanolamin ist in erfindungsgemƤĆen Mitteln vorzugsweise in einer Menge von 0,5 bis 5 Gew.-%, insbesondere in einer Menge von 1 bis 4 Gew.-%, enthalten. In einer anderen AusfĆ¼hrungsform ist das erfindungsgemƤĆe Reinigungsmittel frei von Alkanolamin und Ammoniak.It may also be volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is contained in agents according to the invention preferably in an amount of 0.5 to 5 wt .-%, in particular in an amount of 1 to 4 wt .-%. In another embodiment, the cleaning agent according to the invention is free of alkanolamine and ammonia.
Zur Einstellung und/oder Stabilisierung des pH-Werts kann das erfindungsgemƤĆe Mittel ein oder mehrere Puffersubstanzen (INCI Buffering Agents) enthalten, Ć¼blicherweise in Mengen von 0,001 bis 5 Gew.-%. Bevorzugt sind Puffersubstanzen, die zugleich Komplexbildner oder sogar Chelatbildner (Chelatoren, INCI Chelating Agents) sind. Besonders bevorzugte Puffersubstanzen sind die CitronensƤure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise TrinatriumcitratĀ·2H2O und TrikaliumcitratĀ·H2O.To adjust and / or stabilize the pH, the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H 2 O and tripotassium citrate H 2 O.
Als Verdicker eignen sich alle Ć¼blicherweise in Wasch- und Reinigungsmitteln eingesetzten ViskositƤtsregulatoren, zu denen beispielsweise organische natĆ¼rliche Verdickungsmittel (Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, StƤrke, Dextrine, Gelatine, Casein), organische abgewandelte Naturstoffe (Carboxymethylcellulose und andere Celluloseether, Hydroxyethyl- und -propylcellulose und dergleichen, Kernmehlether), organische vollsynthetische Verdickungsmittel (Polyacryl- und Polymethacryl-Verbindungen, Vinylpolymere, PolycarbonsƤuren, Polyether, Polyimine, Polyamide) zƤhlen.Suitable thickeners are all viscosity regulators customarily used in detergents and cleaners, for example organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, Casein), organic modified natural products (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, gum ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides).
Zu den Polyacryl- und Polymethacryl-Verbindungen zƤhlen beispielsweise die hochmolekularen mit einem Polyalkenylpolyether, insbesondere einem Allylether von Saccharose, Pentaerythrit oder Propylen, vernetzten Homopolymere der AcrylsƤure (INCI-Bezeichnung gemĆ¤Ć International Dictionary of Cosmetic Ingredients der The Cosmetic, Toiletry, and Fragrance Association (CTFA): Carbomer), die auch als Carboxyvinylpolymere bezeichnet werden. Solche PolyacrylsƤuren sind u.a. von der Fa. 3V Sigma unter dem Handelsnamen PolygelĀ®, z.B. PolygelĀ® DA, und von der Fa. BFGoodrich unter dem Handelsnamen CarbopolĀ® erhƤltlich, z.B. CarbopolĀ® 940 (Molekulargewicht ca. 4.000.000), CarbopolĀ® 941 (Molekulargewicht ca. 1.250.000) oder CarbopolĀ® 934 (Molekulargewicht ca. 3.000.000). Weiterhin fallen darunter folgende AcrylsƤure-Copolymere: (i) Copolymere von zwei oder mehr Monomeren aus der Gruppe der AcrylsƤure, MethacrylsƤure und ihrer einfachen, vorzugsweise mit C1-4-Alkanolen gebildeten, Ester (INCI Acrylates Copolymer), zu denen etwa die Copolymere von MethacrylsƤure, Butylacrylat und Methylmethacrylat (CAS-Bezeichnung gemƤĆ
BFGoodrich unter dem Handelsnamen CarbopolĀ® erhƤltlich sind, z.B. das hydrophobierte CarbopolĀ® ETD 2623 und CarbopolĀ® 1382 (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) sowie CarbopolĀ® AQUA 30 (frĆ¼her CarbopolĀ® EX 473). In der internationalen Anmeldung
Weitere Verdickungsmittel sind die Polysaccharide und Heteropolysaccharide, insbesondere die Polysaccharidgummen, beispielsweise Gummi arabicum, Agar, Alginate, Carrageene und ihre Salze, Guar, Guaran, Traganth, Gellan, Ramsan, Dextran oder Xanthan und ihre Derivate, z.B. propoxyliertes Guar, sowie ihre Mischungen. Andere Polysaccharidverdicker, wie StƤrken oder Cellulosederivate, kƶnnen alternativ, vorzugsweise aber zusƤtzlich zu einem Polysaccharidgummi eingesetzt werden, beispielsweise StƤrken verschiedensten Ursprungs und StƤrkederivate, z.B. HydroxyethylstƤrke, StƤrkephosphatester oder StƤrkeacetate, oder Carboxymethylcellulose bzw. ihr Natriumsalz, Methyl-, Ethyl-, Hydroxyethyl-, Hydroxypropyl-, Hydroxypropyl-methyl- oder Hydroxyethyl-methyl-cellulose oder Celluloseacetat. Ein besonders bevorzugter Polysaccharidverdicker ist das mikrobielle anionische Heteropolysaccharid Xanthan Gum, das von Xanthomonas campestris und einigen anderen Spezies unter aeroben Bedingungen mit einem Molekulargewicht von 2-15Ć106 produziert wird und beispielsweise von der Fa. Kelco unter den Handelsnamen KeltrolĀ® und Kelzan Ā® oder auch von der Firma Rhodia unter dem Handelsnamen RhodopolĀ® erhƤltlich ist.Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate. A particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum produced by Xanthomonas campestris and some other species under aerobic conditions having a molecular weight of 2-15 x 10 6 and, for example, by Kelco under the trade names KeltrolĀ® and KelzanĀ® or also available from the company Rhodia under the trade name RhodopolĀ®.
In verschiedenen AusfĆ¼hrungsformen besitzt die zweite flĆ¼ssige Zubereitung direkt nach der Herstellung eine ViskositƤt oberhalb 1000 mPas (Brookfield Viscometer DV-II+Pro, Spindel 25, 30 rpm, 20Ā°C), insbesondere zwischen 2000 und 10000 mPas. Nach der Lagerung kann die ViskositƤt hƶher sein, beispielsweise grƶĆer als 10000 mPas, wie zum Beispiel im Bereich 10000-50000 mPas, (Brookfield Viscometer DV-II+Pro, Spindel 25, 5 rpm, 20Ā°C). Es ist bevorzugt, dass die zweite flĆ¼ssige Zubereitung bei Raumtemperatur flieĆfƤhig ist.In various embodiments, the second liquid preparation has a viscosity above 1000 mPas directly after preparation (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 Ā° C.), in particular between 2000 and 10000 mPas. After storage, the viscosity may be higher, for example greater than 10,000 mPas, such as in the range 10000-50000 mPas, (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 Ā° C). It is preferable that the second liquid preparation is flowable at room temperature.
Die erfindungsgemƤĆen Reinigungsmittel zeichnen sich dadurch aus, dass sie lagerstabil sind und selbst nach einem lƤngeren Zeitraum keine Phasentrennung auftritt.The cleaning agents according to the invention are characterized in that they are stable on storage and even after a prolonged period, no phase separation occurs.
Die (auch als wasserlƶsliche UmhĆ¼llung bezeichnete) wasserlƶsliche Verpackung des Reinigungsmittels, wird vorzugsweise aus einem wasserlƶslichen Folienmaterial, welches ausgewƤhlt ist aus der Gruppe, bestehend aus Polymeren oder Polymergemischen, gebildet. Die Verpackung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlƶslichen Folienmaterial gebildet werden. Das wasserlƶsliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein. Besonders bevorzugt sind Folien, die beispielsweise zu Verpackungen wie SchlƤuchen oder Kissen verklebt und/oder versiegelt werden kƶnnen, nachdem sie mit einem Mittel befĆ¼llt wurden.The water-soluble packaging of the cleaning agent (also referred to as a water-soluble coating) is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The package may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
GemĆ¤Ć einer weiteren bevorzugten AusfĆ¼hrungsform handelt es sich bei der wasserlƶslichen Verpackung um eine wasserlƶsliche Verpackung aus einer Polyvinylalkohol- oder Polyvinylalkoholcopolymer-haltigen Folie. Es ist bevorzugt, dass die wasserlƶsliche Verpackung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthƤlt. Wasserlƶsliche Verpackungen, die Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthalten, weisen eine gute StabilitƤt bei einer ausreichend hohen Wasserlƶslichkeit, insbesondere Kaltwasserlƶslichkeit, auf.According to a further preferred embodiment, the water-soluble packaging is a water-soluble packaging made of a polyvinyl alcohol or polyvinyl alcohol copolymer-containing film. It is preferable that the water-soluble packaging contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble packaging containing polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.
Geeignete wasserlƶsliche Folien zur Herstellung der wasserlƶslichen Verpackung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10.000 bis 1.000.000 gmol-1, vorzugsweise von 20.000 bis 500.000 gmol-1, besonders bevorzugt von 30.000 bis 100.000 gmol-1 und insbesondere von 40.000 bis 80.000 gmol-1 liegt.Suitable water-soluble films for preparing the water-soluble packaging are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
Die Herstellung von Polyvinylalkohol geschieht Ć¼blicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht mƶglich ist. Ćhnliches gilt fĆ¼r Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlƶslichen Verpackung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht.The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble packaging comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
Einem zur Herstellung der wasserlƶslichen Verpackung geeignetem Polyvinylalkohol-enthaltendem Folienmaterial kann zusƤtzlich ein Polymer ausgewƤhlt aus der Gruppe umfassend (Meth)AcrylsƤure-haltige (Co)Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether, PolymilchsƤure oder Mischungen der vorstehenden Polymere zugesetzt sein. Ein bevorzugtes zusƤtzliches Polymer sind PolymilchsƤuren.In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above can be additionally used as a polyvinyl alcohol-containing film material suitable for producing the water-soluble packaging Be added polymers. A preferred additional polymer is polylactic acids.
Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol DicarbonsƤuren als weitere Monomere. Geeignete DicarbonsƤure sind ItaconsƤure, MalonsƤure, BernsteinsƤure und Mischungen daraus, wobei ItaconsƤure bevorzugt ist.Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
Ebenfalls bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesƤttige CarbonsƤure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol AcrylsƤure, MethacrylsƤure, AcrylsƤureester, MethacrylsƤureester oder Mischungen daraus.Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
Es kann bevorzugt sein, dass das Folienmaterial weitere Zusatzstoffe enthƤlt. Das Folienmaterial kann beispielsweise Weichmacher wie Dipropylenglycol, Ethylenglycol, Diethylenglycol, Propylenglycol, Glycerin, Sorbitol, Mannitol oder Mischungen daraus enthalten. Weitere Zusatzstoffe umfassen beispielsweise Freisetzungshilfen, FĆ¼llmittel, Vernetzungsmittel, Tenside, Antioxidationsmittel, UV-Absorber, Antiblockmittel, Antiklebemittel oder Mischungen daraus.It may be preferred that the film material contains further additives. The film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, Propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
Geeignete wasserlƶsliche Folien zum Einsatz in den wasserlƶslichen Verpackungen / den wasserlƶslichen Verpackungen gemĆ¤Ć der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, M8534, C8400 oder M8900 vertrieben werden. Andere geeignete Folien umfassen Folien mit der Bezeichnung SolublonĀ® PT, SolublonĀ® GA, SolublonĀ® KC oder SolublonĀ® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray.Suitable water-soluble films for use in the water-soluble packaging / water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, M8534, C8400 or M8900. Other suitable films include films named SolublonĀ® PT, SolublonĀ® GA, SolublonĀ® KC or SolublonĀ® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
Die erfindungsgemƤĆen Reinigungsmittel kƶnnen als GeschirrspĆ¼lmittel, insbesondere maschinelle GeschirrspĆ¼lmittel (MaschinengeschirrspĆ¼lmittel) verwendet werden. Die entsprechende Verwendung ist ebenfalls Gegenstand der Erfindung. Ebenso betrifft die Erfindung ein GeschirrspĆ¼lverfahren, insbesondere maschinelles GeschirrspĆ¼lverfahren, bei welchem ein Reinigungsmittel gemĆ¤Ć der Erfindung eingesetzt wird. Die vorstehend beschriebenen besonderen AusfĆ¼hrungsformen gelten auch fĆ¼r die Verwendung bzw. das Verfahren.The cleaning agents according to the invention can be used as dishwashing detergents, in particular automatic dishwashing detergents (machine dishwashing detergents). The corresponding use is also the subject of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used. The particular embodiments described above also apply to the use or the method.
Bei den erfindungsgemƤĆen Reinigungsmitteln handelt es sich vorzugsweise um ein GeschirrspĆ¼lmittel, insbesondere um ein maschinelles GeschirrspĆ¼lmittel.The cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.
Angegebene Mengen sind Aktivsubstanz (soweit nichts anderes angegeben).
Es wurde eine besonders stabile Dispersion in der ersten flĆ¼ssigen Phase (Kammer I) erhalten, die auch nach einer Lagerzeit von 4 Wochen bei 40Ā°C keine Sedimentation der Soda aufwies.There was obtained a particularly stable dispersion in the first liquid phase (chamber I), which had no sedimentation of the soda even after a storage time of 4 weeks at 40 Ā° C.
Das erfindungsgemƤĆe vorportionierte Reinigungsmittel, welches in einem Zweikammerpouch (Zweikammerbeutel) aus PVA-haltiger Folie bereitgestellt wurde und 5 g der ersten flĆ¼ssigen Phase (Kammer I) und 15 g der zweiten flĆ¼ssigen Phase (Kammer II) enthielt, zeigte bei einem Einsatz in einer herkƶmmlichen SpĆ¼lmaschine eine gute Reinigungsleistung auf angebrannten Anschmutzungen im Vergleich zu einem handelsĆ¼blichen vorportionierten flĆ¼ssigen Reinigungsmittel in einem Einkammerpouch.The pre-portioned detergent according to the invention, which was provided in a Zweikammerpouch (two-chamber bag) of PVA-containing film and 5 g of the first liquid phase (chamber I) and 15 g of the second liquid phase (chamber II) contained when used in a conventional Dishwasher a good cleaning performance on burnt stains compared to a commercially available pre-portioned liquid detergent in a Einkammerpouch.
Angegebene Mengen sind Aktivsubstanz (soweit nichts anderes angegeben).
Es wurde keine stabile Dispersion in der ersten flĆ¼ssigen Phase (Kammer I) erhalten; bereits nach wenigen Stunden Lagerung bei Raumtemperatur zeigte sich eine Sedimentation des Natriumcarbonats (Soda).There was no stable dispersion in the first liquid phase (chamber I); After only a few hours of storage at room temperature, sedimentation of the sodium carbonate (soda) was observed.
Claims (13)
- A pre-portioned cleaning agent, preferably a dishwashing detergent, in a water-soluble packaging having at least two compartments, comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation contains alkali metal carbonate, preferably sodium carbonate, in an amount of from 20 to 60 wt.%, and further contains a magnesium-containing phyllosilicate in an amount of from 0.01 to 10 wt.%, in each case based on the total weight of the first liquid preparation.
- The cleaning agent according to claim 1, characterized in that the phyllosilicate is contained in the first liquid preparation in an amount of from 0.1 to 8 wt.%, in particular 0.3 to 5 wt.%, most particularly preferably 0.6 to 3 wt.%, in each case based on the total weight of the first liquid preparation.
- The cleaning agent according to one of claims 1 to 2, characterized in that the first liquid preparation further contains at least one non-ionic surfactant, preferably selected from the group of the alkoxylated alcohols.
- The cleaning agent according to claim 3, characterized in that the first liquid preparation contains between 1 and 75 wt.%, preferably 5 to 60 wt.%, more preferably 10 to 50 wt.%, in each case based on the total weight of the first liquid preparation, of non-ionic surfactant.
- The cleaning agent according to one of claims 3 or 4, characterized in that the first liquid preparation contains a component according to formula (I)
āāāāāāāāR1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x(CH2-CH(R4)-O)y(CH2-CH(R5)-O)z-R6
where R1 is selected from straight-chain or branched, saturated C8-16 alkyl functional groups; R2 and R4 are -H, and R3 and R5 are -CH3,R6 is selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, - CH2CH(CH3)2, -C(CH3)3, C5-20 alkyl (linear or branched), and, selected independently of one another,w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;x = 0 to 6, preferably 1.5 to 4.5, in particular 2 to 3;y = 0 to 6, preferably 1.5 to 4.5, in particular 2 to 3;z = 0 to 6, preferably 1.5 to 4.5, in particular 2 to 3,as the non-ionic surfactant. - The cleaning agent according to one of claims 1 to 5, characterized in that the liquid preparations each contain one or more solvents, preferably propanediols, 1,2-propanediol and/or 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycol, glycerol, and/or a mixture thereof, in particular 1,2-propanediol and/or glycerol.
- The cleaning agent according to one of claims 1 to 6, characterized in that the ratio of the water content of the first and the second liquid preparations with respect to one another, in each case based on the total weight of the relevant liquid preparation, is between 5:1 and 1:5.
- The cleaning agent according to one of claims 1 to 7, characterized in that one of the liquid preparations, preferably at least the second liquid preparation, further contains at least one builder or co-builder, in particular selected from the group formed from citrate, aminocarboxylates, in particular MGDA and/or GLDA, polyphosphates, preferably a tripolyphosphate, as well as phosphonates and mixtures thereof.
- The cleaning agent according to one of claims 1 to 8, characterized in that one of the liquid preparations, preferably the second liquid preparation, further contains one or more substances selected from the group consisting of pH adjusters, anionic, cationic and amphoteric surfactants, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, bitter principles, fragrances and antimicrobial active ingredients.
- The cleaning agent according to one of claims 1 to 9, characterized in that the first liquid preparation is substantially free of enzymes, i.e. contains less than 1 wt.%, in particular less than 0.1 wt.%, of enzyme preparation.
- The cleaning agent according to one of claims 1 to 10, characterized in that it involves a water-soluble packaging consisting of a film containing polyvinyl alcohol or polyvinyl alcohol copolymer.
- The use of the cleaning agent according to one of claims 1 to 11 as a dishwashing detergent, in particular as an automatic dishwashing detergent.
- An automatic dishwashing method, characterized in that a cleaning agent according to one of claims 1 to 11 is used.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL15708188T PL3114198T3 (en) | 2014-03-06 | 2015-03-04 | Pre-portioned cleaning agent comprising at least two separate liquid preparations |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102014204144.9A DE102014204144A1 (en) | 2014-03-06 | 2014-03-06 | Pre-portioned detergents comprising at least two separate liquid preparations |
PCT/EP2015/054463 WO2015132279A1 (en) | 2014-03-06 | 2015-03-04 | Pre-portioned cleaning agent comprising at least two separate liquid preparations |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3114198A1 EP3114198A1 (en) | 2017-01-11 |
EP3114198B1 true EP3114198B1 (en) | 2019-10-30 |
Family
ID=52629564
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15708188.6A Active EP3114198B1 (en) | 2014-03-06 | 2015-03-04 | Pre-portioned cleaning agent comprising at least two separate liquid preparations |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP3114198B1 (en) |
DE (1) | DE102014204144A1 (en) |
PL (1) | PL3114198T3 (en) |
WO (1) | WO2015132279A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB201419691D0 (en) * | 2014-11-05 | 2014-12-17 | Armstrong John S | Apparatus method and substance for washing glassware and/or dishware |
US11434454B2 (en) | 2017-12-22 | 2022-09-06 | Church & Dwight Co., Inc. | Laundry detergent composition |
EP3770241A1 (en) | 2019-07-22 | 2021-01-27 | Henkel AG & Co. KGaA | Cleaning agent with protease for automatic dosing |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5004556A (en) * | 1987-06-17 | 1991-04-02 | Colgate-Palmolive Company | Built thickened stable non-aqueous cleaning composition and method of use |
US5798324A (en) | 1996-04-05 | 1998-08-25 | S.C. Johnson & Son, Inc. | Glass cleaner with adjustable rheology |
WO2002006438A1 (en) * | 2000-07-19 | 2002-01-24 | The Procter & Gamble Company | Gel form automatic dishwashing compositions, methods of preparation and use thereof |
US6228825B1 (en) * | 2000-10-13 | 2001-05-08 | Colgate Palmolive Company | Automatic dishwashing cleaning system |
DE102005041708A1 (en) * | 2005-09-02 | 2007-03-08 | Henkel Kgaa | cleaning supplies |
US20110240510A1 (en) * | 2010-04-06 | 2011-10-06 | Johan Maurice Theo De Poortere | Optimized release of bleaching systems in laundry detergents |
-
2014
- 2014-03-06 DE DE102014204144.9A patent/DE102014204144A1/en not_active Withdrawn
-
2015
- 2015-03-04 PL PL15708188T patent/PL3114198T3/en unknown
- 2015-03-04 EP EP15708188.6A patent/EP3114198B1/en active Active
- 2015-03-04 WO PCT/EP2015/054463 patent/WO2015132279A1/en active Application Filing
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
PL3114198T3 (en) | 2020-04-30 |
DE102014204144A1 (en) | 2015-09-10 |
EP3114198A1 (en) | 2017-01-11 |
WO2015132279A1 (en) | 2015-09-11 |
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