EP0888450A2 - Wasch- oder reinigungsmitteladditiv sowie ein verfahren zu seiner herstellung - Google Patents
Wasch- oder reinigungsmitteladditiv sowie ein verfahren zu seiner herstellungInfo
- Publication number
- EP0888450A2 EP0888450A2 EP97933648A EP97933648A EP0888450A2 EP 0888450 A2 EP0888450 A2 EP 0888450A2 EP 97933648 A EP97933648 A EP 97933648A EP 97933648 A EP97933648 A EP 97933648A EP 0888450 A2 EP0888450 A2 EP 0888450A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- additive
- weight
- bleach
- granular
- acid
- 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.)
- Granted
Links
- 239000000654 additive Substances 0.000 title claims abstract description 90
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 37
- 238000005406 washing Methods 0.000 title claims abstract description 28
- 230000000996 additive effect Effects 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000008187 granular material Substances 0.000 claims abstract description 73
- 239000007844 bleaching agent Substances 0.000 claims abstract description 63
- 239000012190 activator Substances 0.000 claims abstract description 36
- 239000003112 inhibitor Substances 0.000 claims abstract description 34
- 239000006260 foam Substances 0.000 claims abstract description 32
- 239000004615 ingredient Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims description 45
- 239000003945 anionic surfactant Substances 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000003599 detergent Substances 0.000 claims description 23
- 102000004190 Enzymes Human genes 0.000 claims description 22
- 108090000790 Enzymes Proteins 0.000 claims description 22
- 238000005469 granulation Methods 0.000 claims description 17
- 230000003179 granulation Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000004061 bleaching Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 11
- 150000001450 anions Chemical class 0.000 abstract description 2
- -1 alkyl sulfate compounds Chemical class 0.000 description 55
- 239000002585 base Substances 0.000 description 38
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 31
- 229940088598 enzyme Drugs 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 21
- 229920002245 Dextrose equivalent Polymers 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 18
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- 238000009826 distribution Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000002736 nonionic surfactant Substances 0.000 description 14
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229920002472 Starch Polymers 0.000 description 11
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 150000004760 silicates Chemical class 0.000 description 11
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- 230000008569 process Effects 0.000 description 10
- 239000003760 tallow Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 108091005804 Peptidases Proteins 0.000 description 9
- 239000004365 Protease Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 150000008051 alkyl sulfates Chemical class 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 159000000000 sodium salts Chemical class 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
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- 239000004367 Lipase Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 235000019421 lipase Nutrition 0.000 description 7
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 7
- 239000004375 Dextrin Substances 0.000 description 6
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- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000019425 dextrin Nutrition 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
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- 235000019419 proteases Nutrition 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- 230000002940 repellent Effects 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 235000000346 sugar Nutrition 0.000 description 6
- 108010059892 Cellulase Proteins 0.000 description 5
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- 235000013162 Cocos nucifera Nutrition 0.000 description 5
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 229940106157 cellulase Drugs 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Chemical class 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000013065 commercial product 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
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 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
- 102000004157 Hydrolases Human genes 0.000 description 4
- 108090000604 Hydrolases Proteins 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
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- 239000008103 glucose Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000002366 lipolytic effect Effects 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
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- 238000005204 segregation Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
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- 235000011152 sodium sulphate Nutrition 0.000 description 4
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- 150000003624 transition metals Chemical class 0.000 description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
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- 229910019142 PO4 Inorganic materials 0.000 description 3
- 102000035195 Peptidases Human genes 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
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- 239000003513 alkali Substances 0.000 description 3
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
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- 150000008163 sugars Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
Definitions
- the invention relates to a detergent or cleaning agent additive which contains, in particular, customary admixing components of modern washing or cleaning agents, as well as a process for its preparation and the washing or cleaning agents which can be obtained by admixing these additives.
- modern washing or cleaning agents are understood to mean those that have rubble weights of at least 500 g / l
- Granular detergents or cleaning agents with debris weights above 500 g / l are now part of the state of the art.
- the products available on the market usually consist of at least one compound or several compounds, one basic granulate or several basic granules and other admixing components, either because of their temperature sensitivity or their sensitivity to water or because of undesired interactions with other ingredients cannot be used in the manufacturing process of the basic granules.
- These are in particular solid ingredients such as bleach activators, so-called Soi! Repellents, foam inhibitors, but also enzymes.
- Anionic surfactants, for example, which are not suitable for use in larger quantities in a slurry for spray drying, have already been described as compounds which were subsequently mixed with other compounds or basic granules.
- These solids can be finely divided up to Granularly present, however, they usually differ in their weight, their grain shape and / or in their particle size distribution, both among themselves and with respect to the base granules or the base granules.
- the individually admixed components generally have a significantly lower bulk weight than the base granules or the base granules and do not only different grain sizes, but also different grain shapes and different surface properties than the basic granules.
- the added components generally lead to a reduction in the bulk weight of the finished product ts, compared to the debris weight of the base granules or the base granules
- These (and other properties) cause the known problem of segregation, so that - especially after transport and storage - an uneven distribution of the ingredients in the finished washing or cleaning agent is obtained, which the finished Product not only a disadvantage because it gives an optically uneven appearance, but can also lead to disadvantages in use, since it can no longer be ensured that the distribution of the individual components is homogeneous on average.
- an inhomogeneous distribution on average also became an inhomogeneous distribution these ingredients result in the individual package so that the consumer at Using the same package would apply different compositions, which could result in significantly different washing results
- Another problem is the homogeneous distribution of the solid small components, that is, those ingredients that are only added to the basic granules in amounts of about 0.1 to 4% by weight.
- it is precisely the admixture and the homogeneous distribution of these Small components in the mixture understandably have a relatively high error
- the invention was therefore based on the object of providing granular detergents or cleaning agents with debris weights of at least 500 g / l which do not have the disadvantages mentioned above
- the invention therefore relates to a granular additive with a bulk density of at least 500 g / l, which is suitable for use in granular washing or cleaning agents with bulk densities of at least 500 g / l, this additive comprising one or more anionic surfactants and at least one contains a further constituent which is usually added subsequently in the production of detergents or cleaning agents, with the proviso that the additive contains at least one constituent selected from bleach activator, bleach catalyst and pre-assembled foam inhibitor in addition to the anionic surfactant (s), where the prefabricated foam inhibitor is preferred
- the invention relates to a method for producing a granular additive with a debris weight of at least 500 g / l, which is suitable for use in granular washing or cleaning agents with a debris weight of at least 500 g / l, wherein an additive which is uniform in composition, grain size and grain shape is produced by granulating, compacting or extruding and one or more anionic (s) and at least one further constituent are used for the preparation of the additive and are usually added subsequently in the production of washing or cleaning agents , with the proviso that at least one component selected from bleach activator, bleach catalyst and pre-assembled foam inhibitor is used in addition to the anion (s), but at least one component is introduced into the process in pre-assembled form
- Another object of the invention is a granular washing or cleaning agent with a bulk density of at least 500 g / l, which contains conventional ingredients including anionic surfactants and foam inhibitors and optionally bleaching agents, bleach activators and / or bleaching catalysts,
- the additive according to the invention has at least one further constituent which is usually contained in washing or cleaning agents.
- additives are preferred which contain anionic surfactant (s), pre-assembled foam inhibitor and bleach activator and / or bleach catalyst.
- the additive according to the invention is preferably not limited to a specific grain size, grain shape and certain surface properties and to a specific bulk density, but can be prepared in such a way that it constitutes (admixed) granules adapted to the base granules or the base granules in terms of bulk density, grain size and grain shape.
- a common test for measuring the flow behavior is to fill 1 liter of the sample to be measured into a powder funnel, which is initially closed at its outlet direction, and then measure the outlet time of the samples compared to dry sea sand.
- the discharge time of the dry sea sand after the discharge opening has been released (13 seconds) is set to 100%.
- the flow behavior of the samples to be examined is given in%, based on 100% (measured on sea sand).
- the flow behavior - determined according to the test described above - of the additive is set such that it does not differ from the flow behavior of the base granulate or the sum of the base granules by more than 20% points, preferably not more than 10% points .
- the additive according to the invention contains at least anionic surfactants, preferably alkyl sulfates (for a further description of possible surfactants, see below in the general description section), and preferably as additives usually contained in detergents or cleaning agents.
- anionic surfactants preferably alkyl sulfates (for a further description of possible surfactants, see below in the general description section)
- additives usually contained in detergents or cleaning agents.
- foam inhibitors in pre-assembled solid form further possible components are, in addition to the preferred bleach activators or bleach catalysts, also peroxy bleaches, but also, for example, enzymes and so-called soil repellents
- Suitable anionic surfactants which are used in the additive according to the invention are, in particular, alk (en) yl sulfates, including 2,3-alkyl sulfates and alkylbenzenesulfonates (for a more detailed description, see below). They are also preferably used in prefabricated, in particular in granular form, anion surfactant compounds with active substance contents above 60% by weight are particularly preferred.
- alkyl sulfate compounds with 70 to 90% by weight (optionally also above) active substance which contain sodium sulfate and / or sodium carbonate, unsulfated components and water as other constituents and C-chain cuts with at least 90% by weight, preferably with at least 95% by weight C12-C18, which are more than 50% by weight Cie-C-i ⁇ and at least 20% by weight, are of particular interest. have less than Ci6
- the anionic surfactant content of the additives according to the invention, in particular in front prefabricated form is preferably 20 to 60% by weight and in particular at least 30% by weight
- Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-C24 fatty acids.
- Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, possibly silanized, silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized Silicic acid or bistearylethylene diamide Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
- the foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are used in a ready-made and solid form, these preferably being in a form granular, water-soluble or dispersible carrier substance are bound.
- foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors
- these preferably being in a form granular, water-soluble or dispersible carrier substance are bound.
- mixtures of paraffins and bistearylethylene diamides are preferred.
- the content of solid foam inhibitor compound in the additives according to the invention nds is preferably 1 to 25% by weight and in particular 5 to 20% by weight.
- the weight ratio of anionic surfactants to pre-assembled foam inhibitor can vary within a wide range in the additives according to the invention. It is also possible that the weight ratio of anionic surfactants to pre-assembled foam inhibitor is less than 1.
- the additives have j edoch anionic surfactants and foam inhibitors in a pre-assembled perennialsverhaltms of 5 1 up to 1 1, preferably from 1 to 4 1, 5 1, in particular from 3.5 1 to 2 1 to It is particularly preferred that the inventive additives 30 to 70 % By weight of a highly concentrated anionic surfactant compound and 10 to 30% by weight, advantageously 12 to 25% by weight of a pre-assembled foam inhibitor
- the additives according to the invention can also contain bleach activators or bleach catalysts
- Compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid and / or optionally substituted perbenzoic acid can be used as bleach activators.
- Substances containing O- and / or N are suitable -Acyl groups of the abovementioned carbon atoms and / or optionally substituted benzoyl groups are preferred.
- Polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated t ⁇ azine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5- t ⁇ az ⁇ n (DADHT), acylated glycol, especially tetraacetylglycol (TAGU), N-acylimide, especially N-nonanoylsuccinimide, especially n-nonanoyl- or isononanoyloxybenzene-sulfonate, nOBurson acylated polyhydric alcohols, in particular T ⁇ acetin, ethylene glycol diacetate, 2,5-D ⁇ acetoxy-2,5-d ⁇ hydrofuran and di e known from the German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described
- hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and those in US Pat German patent application DE 196 16 770 and the international patent application WO 95/14075 acyl lactams described are also preferably used.
- the Ko known from German patent application DE 44 43 177 Combinations of conventional bleach activators can be used.
- Such bleach activators are in the usual range of amounts, preferably in amounts of 1% by weight to 10% by weight. contain in particular 2% by weight to 8% by weight, based on the total agent, in the additive according to the invention the content of bleach activator, preferably of pre-assembled bleach activator, is advantageously 10 to 50% by weight, in particular at least 20% by weight
- the sulfonimines and / or bleach-intensifying transition metal salts or transition metal complexes or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 can also be present as so-called bleaching catalysts.
- the transition metal compounds in question include in particular those manganese, iron, cobalt, ruthenium or molybdenum salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, the manganese known from German patent application DE 195 36 082 -, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper described in the German patent application DE 196 05 688 Complexes with nitrogen-containing T ⁇ pod ligands, which from German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium amm complexes, the manganese, copper and cobalt complexes described in German patent application DE 44 16 438, the cobalt complexes described in European patent application EP 0 272 030 Complexes, the manganese complexes known from European patent application EP
- Manganese complexes described in EP 0 544 519 combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
- Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo , V, Ti and / or Ru are used in conventional amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight up to 0.1% by weight, based in each case on the total average.
- Their content in the additives according to the invention can be, for example, 0.5 to 5% by weight, preferably less than 3% by weight - 1 -
- the bleach activator into the process for producing the additive in a pre-assembled form.
- the bleach activator can be coated with shell substances in a known manner or, if appropriate using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, granulated or extruded before use / have been pelleted and, if desired, contain further additives, for example dye, preferably contain such granules in excess of 70% by weight, in particular 90 to 99% by weight, of bleach activator.
- the additive according to the invention preferably contains a bleach activator which forms peracetic acid under washing conditions
- the weight ratio (based on active substance contents) of anionic surfactants to bleach activators and, if appropriate, bleaching catalysts is 0.5 1 to 2 1 and in particular 0.9 1 to 1, 5 1.
- one according to the invention contains Additive 30 to 60% by weight of a highly concentrated anionic surfactant compound and 25 to 40% by weight of a likewise highly concentrated bleach activator compound
- Soii repellents but also plasticizers, known substances which contribute to the improvement of solubility, dyes and fragrances, optionally also enzymes and parts of the bullder system, which are usually present in amounts of up to a maximum of 10, are among the further possible ingredients of the compounds according to the invention % By weight, preferably up to a maximum of 8% by weight and in particular in amounts below 5% by weight, in each case based on the finished composition
- So-called soil repellents may contain components which have a positive effect on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is contaminated which has already been washed several times beforehand with a detergent according to the invention which contains this oil- and fat-free component
- Non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight each include, for example, the preferred oil- and fat-dissolving components based on the nonionic cellulose ether, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these particularly preferred of these are di e sulfonated den- vate of phthalic and tere
- the additives according to the invention preferably contain such soil repellents (optionally in pre-assembled form), which are usually used in the finished product in amounts of 0.2 to less than 5% by weight, in amounts of 1 to 8% by weight and in particular in amounts of 2 to 6% by weight
- the flow agents which can be used to improve the flow behavior are, in particular, the known silicas, silicic acid derivatives, but also aluminosilicates such as zeolite A, X and / or P.
- Their content in the additives is preferably not more than 3% by weight.
- the additives contain dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches Hydrolysis can be carried out by customary, for example acid- or enzyme-catalyzed, processes. It is preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
- DE dextrose equivalent
- the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of at least one alcohol function or to oxidize an aldehyde function of the saccharide to the carboxylic acid function.
- oxidizing agents capable of at least one alcohol function or to oxidize an aldehyde function of the saccharide to the carboxylic acid function.
- Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A -0 542 496 and international patent applications WO-A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A- 95/07303, WO-A-95/12619 and WO- A-95/20608 known
- a product oxidized at C 6 of the saccharide can be particularly advantageous
- Suitable builder substances are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as are described, for example, in US Pat international patent application WO-A-93/08251 or the production thereof is described, for example, in international patent application WO-A-93/16110. Oxidized oligosaccharides according to the older German patent application P 196 00 018.1 are also suitable.
- the additives can also contain oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
- oxydisuccinates and other derivatives of disuccinates preferably ethylenediamine disuccinate.
- glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 become. Suitable amounts used are 3 to 15% by weight in formulations containing zeolite and / or silicate.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
- Such cobuilders are described, for example, in international patent application WO-A-95/20029.
- Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
- Suitable copolymeric polycarboxylates are, 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 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred; in the latter case they serve as granulation aids (see below).
- biodegradable polymers made up of more than two different monomer units, for example those which according to DE-A-43 00 772 Monomeric salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives
- copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably have acrolem and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers
- the content of (co) polymeric polycarboxylates in the finished, optionally dried additive is preferably 1 to 5% by weight. If desired, the content of these organic cobuilders can also be higher amounts, which exceed this 5% by weight Advantageously, in solid form and not introduced into the additive via the granulation liquid.
- Polymeric aminodicarboxylic acids, their salts or their precursor substances are also to be mentioned as further preferred builder substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE-A -195 40 086 discloses that, in addition to cobuilder properties, they also have a bleach-stabilizing effect
- polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
- Preferred polyacetals obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid
- the additives can, of course, also include the polycarboxylic acids which are visible, for example, in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acids, nitric acid acetic acid (NTA), provided that such use is not objectionable for ecological reasons and for mixtures from these contain Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures of these
- the acids themselves can also be used.
- the acids typically also have the property of an acid component and thus also serve to set a lower and milder pH value of washing or Cleaning agents
- citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned
- the organic builder substances in the additives according to the invention are preferably 0.1 to 15% by weight.
- Further ingredients are preferably phosphonates, which are usually used in finished compositions in amounts of 0.1 to normally not more than 2.5% by weight.
- their content in the additives according to the invention is preferably more than 1% by weight and in particular 1.5 up to 5% by weight
- the additives can also be provided with colorants and fragrances, which are then usually applied in liquid form
- Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains in the wash, such as stains containing protein, fat or starch, and graying in the case of cellulases and other glycosyl hydrolases, by removing pilling and microfibels, can contribute to color retention and increase the softness of the textile. Oxidoreductases can also be used to bleach or inhibit color transfer
- Enzymatic active ingredients obtained from bacterial strains or fungi such as Ba ⁇ llus subtihs, Bacillus lichemformis, Streptomyces g ⁇ seus and Humicola insolens are particularly preferred.
- Proteases of the sub-sin type and in particular proteases obtained from Bacillus lentus are used.
- lipolytically active enzymes are the known cutinases.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- Suitable Amy read especially ⁇ -amylases, iso-amylases, pullulanases and pectinases.
- Cellobiohydrolases, E ⁇ doglucanases and ß-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases
- the enzymes can be adsorbed on carriers and / or embedded in shell substances in order to protect them against premature decomposition. If enzymes are used in the additives according to the invention, the proportion of the enzymes, enzyme mixtures or enzyme granules is preferably 5 to 30% by weight, in particular 8 to 20% by weight
- the bulk weight of the additives according to the invention is preferably in a range between 550 and 1000 g / l.
- the bulk weight of the additive according to the invention is not more than ⁇ 150 g / l, advantageously not more than 100 g / l, of the bulk weight of the base granules or the base granules deviate
- the additives are usually in granular form.
- the particle size distribution can - as is usual with granules - cover a broad spectrum.
- the spectrum of the particle size distribution can also be influenced by the use of pre-assembled ingredients.This means that not only the aesthetics of the finished product can be affected If the spectrum of the particle size of the additives is adapted to the spectrum of the particle size of the base granules, the tendency towards segregation in the finished agent can be considerably reduced
- the additives according to the invention deviate from the spherical shape by at most 20 area%, in particular at most 10 area%, the deviation being measured using the method of silhouette projection.
- This measurement method can be used, for example the "particle size device 3" from Zeiss.
- the deviation from the spherical shape is determined here by the percentage of the area outside a circle with the same total area as the projected image of the granulate
- the additive contains anionic (s), pre-assembled foam inhibitor and bleach activator and / or bleach catalyst. It is particularly preferred that, in addition to the foam inhibitors, the anionic surfactants and bleach activators or bleach catalysts are used in pre-assembled, preferably granular form
- the inventive additives accordingly contain bleach and / or bleach catalyst, anionic surfactants, preferably alk (en) yl sulfates including 2 3-alkyl sulfates and / or alkyl benzene sulfonates (more detailed description see below) and foam inhibitors especially j in each case in preformulated form
- the additive according to the invention contains all components which are usually admixed in solid form to form a base granulate or a plurality of base granules, which in total up to 30% by weight, preferably up to 25% by weight and in particular at least 10% by weight. Make up% of the finished detergent or cleaning agent
- the additives according to the invention contain bleach activators and, if appropriate, bleach catalysts, anionic surfactants and foam inhibitors in amounts of at least 50% by weight (based on active substance).
- bleach activators and, if appropriate, bleach catalysts, anionic surfactants and foam inhibitors in amounts of at least 50% by weight (based on active substance).
- 70 to 100% by weight of the additives according to the invention come from pre-assembled forms
- These raw materials mentioned exist as “full materials”, the further usually mixed components of detergents or cleaning agents, in particular soil repellents and builders (including alkali carbonates and alkali silicates) and enzymes, but also inorganic salts such as sodium sulfate.
- the water content of the additives is preferably below 10% by weight -% and especially below 8% by weight
- Basic granules are understood to mean those compounds which, when used in their own right, constitute a detergent and usually contain at least surfactants, builder substances and, if appropriate, peroxy bleaching agents. These ingredients must be present not contained in a single base granulate, but can also be distributed among different compounds. A detailed list of the ingredients preferably used in the base granules will be given later
- the additive according to the invention is preferably prepared by batchwise or continuously granulating its ingredients, the latter being processed in a mixer / granulator with the addition of a small amount of granulating liquid to give a possibly moist granulate, which - if spherical or pearl shape is desired - compact in a fillet and can round and optionally subsequently, especially in a fluidized bed, dries
- Known apparatus for example granulators from Gebruder Lodige, Paderborn, can be used as a mixer / granulator.
- Apparatus suitable for compacting and rounding are also known.
- An example is the rounder known under the name "Marume ⁇ zer (R)" Apparatus are described in GB-PS 1 517 713.
- Also known rounding plates or circular discs can be used for rounding.
- a rotating fluidized bed granulator such as that found in Pietsch, "Size Enlargement by Agglomeration", John Wiley & Sons 1990 S 451 is described, application
- a large number of compounds can be used as granulating auxiliaries.
- Compounds from the class of water-soluble cellulose ethers, starches and starch ethers can be used.
- Additives such as oxidation-stable complexing agents and stabilizers for per compounds and / or or further constituents of detergents and cleaning agents are mixed in or introduced via the aqueous granulating liquid.
- salts of polyphosphonic acids such as 1-hydroxyethane-1, 1-diphosphonate, ethylenediamine-tetramethylenephosphonate and diethylenetriamine-pentamethylenephosphonate, each in the form of the sodium salt well-known and suitable additives in the granulation liquid are tallow alcohol sulfates and ethoxylated tallow alcohol sulfates (with up to 100 EO), starch phosphate soaps and known emulsifying agents!
- an aqueous solution of (co) polymeric polycarboxylates is used as the granulation aid.
- copolymers of acrylic acid and maleic acid as well as biodegradable polymers of more than 2 monomer units have proven to be suitable
- aqueous solutions of, in particular, inorganic salts can advantageously be aqueous alkali silicate solutions, preferably sodium silicate solutions, silicates with a Na2 ⁇ SiO 2 ratio of about 1 2 to 1 3, in particular up to 1 2 6, being used.
- aqueous polymer solutions of the type described above have been used and aqueous alkali silicate solutions as granulation aids are particularly preserved
- the amount of water-containing granulation aid is advantageously such that no drying is required after the granulation, in this case water-containing granulation aid is in particular not used in amounts above 5% by weight, amounts between 0.1 and 2.5% by weight. % are particularly preferred.
- the amounts given are based on the total amount of the optionally moist and non-dried granulate. If drying is carried out afterwards, the content of aqueous granulating fluid can also be more than 10 parts by weight, based on 100 parts by weight of the solid mixture to be granulated Usually, however, no more than 15 parts by weight of aqueous granulation liquid are used, values between 8 and 12 parts by weight being particularly advantageous
- the granulation is carried out in an anhydrous manner, that is to say with water-free granulating auxiliaries.
- the nonionic surfactants which are liquid at the processing temperature are particularly suitable, especially ethoxy-hard (fatty) alcohols with a melting point below 40 ° C. , but also polyethylene glycols with molecular weights between 200 and 100,000, the latter advantageously being used in combination with nonionic surfactants or in aqueous solution / dispersion
- the abovementioned additives in particular an aqueous solution of a granule auxiliary, or other ingredients of detergents and cleaning agents when rounding the moist ones Granules are added at the same time, for example, they are sprayed in.
- no liquid is added in this process stage dusty fractions are treated, whereby the flow behavior of the granules can be further improved.
- aluminosilicates such as amorphous and / or crystalline zeolite and / or calcium stearate and / or silica
- the fine and / or coarse fractions are screened off, if appropriate after drying, and are returned to the granulation after the coarse fractions have been comminuted
- a washing or cleaning agent By mixing one or more base granules as defined above with the additive according to the invention, a washing or cleaning agent is obtained in which the admixing components are evenly distributed and remain evenly distributed and which has an optically uniform appearance and can also have an increased bulk density
- An increased debris weight is understood here to mean that the debris weight of the agent according to the invention is higher than that of an agent with the same composition and the same base granules (s), but in which the admixing components are not added in compounded form
- the base granules contain in particular surfactants, especially anionic surfactants, nonionic surfactants, optionally also cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants, and also builder substances, peroxy bleaching agents
- a base granulate is processed with 10 to 40% by weight of an additive according to the invention, it being particularly preferred that no more than 10% by weight, advantageously less than 5, of these two components %
- further constituents in particular enzymes, are admixed.
- the base granules are in extruded form and part of the anionic surfactants according to the teaching of German application DE-A-195 19 139 have now proven to be particularly advantageous additives according to the invention are admixed
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type
- Preferred surfactants of the sulfonate type are Cg-C-13-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from Ci2-Ci8-monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
- alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Moles of glycerol can be obtained.
- the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
- sulfonated fatty acid salts As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
- Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C ⁇ - to Ci ⁇ fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semi-esters of the Ci2-C-i8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C- ⁇ o-C2o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
- alk (en) yl sulfates of said chain length which contain a synthetic, linear alkyl chain based of petrochemical having behave similar degradation ⁇ to the corresponding compounds based on oleochemical raw materials.
- Ci6-Ci8-alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C-
- the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 2 -C 14-fatty alkyl sulfates or C 1 -C 8 -alkyl fatty sulfates with C 1 -C-fatty alkyl sulfates and in particular C 1 -C 6 fatty alkyl sulfates with C 6- Ci8 fatty alkyl sulfates.
- not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably Ci6 to C22 are used.
- the total alk (en) yl sulfate content of the detergents is preferably 15 to 25% by weight.
- 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN (R) , are also suitable anionic surfactants.
- 2-Ci8 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight.
- Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C-
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
- Ci2-Ci8 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are particularly preferred.
- Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-diethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
- the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
- R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 4 represents a linear, branched or cyclic alkyl radical or an aryl
- R is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
- [Z] for one linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical [Z] is also here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or Obtaining xylose
- the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an
- Gemim surfactants come into consideration as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer” Carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are generally distinguished by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water In exceptional cases, however, the term gemini surfactants means not only dimeric but also trimeric surfactants
- Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and thermal alcohol tns sulfates and ether sulfates according to older German patent application P 195 03 061 3 end group-blocked dimeric and trimeric mixed ethers according to old- Ren German patent application P 195 13 391 9 are characterized in particular by their bi- and multifunctionality.
- the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes
- Gemim-polyhydroxyfatty acid amides or poly-polyhydroxyfatty acid amides as described in international patent applications WO-A-95/1953, WO-A-95/19954 and WO95-A- / 19955, can also be used
- the base granules preferably contain zeo the and / or silicates, but if appropriate also “and / or” conventional phosphates, especially tripolyphosphates, the latter in particular already in amounts of up to 10% by weight, based on that entire agent, to significant improvements in washing performance when used in combination with zeolite and / or silicates
- the zeolite used which is fine-grain, synthetic and contains bound water is preferably zeolite A and / or P.
- Zeolite MAP ⁇ R commercial product from Crosfield
- zeolite NaP commercial product from Degussa
- zeolite X is also suitable as well as mixtures of A, X and / or P
- the zeolite can be used as a spray-dried powder or also as an undried stabilized suspension which is still moist from its production.
- the zeolite in the event that the zeolite is used as a suspension, it can contain minor additives contain nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-C-
- Suitable substitutes or partial substitutes for phosphates and zeo the are crystalline, layer-like sodium silicates of the general formula NaMS ⁇ x ⁇ 2 ⁇ + ⁇ yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline layered silicates of the formula given are those in which M is Sodium stands and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicate a2S-2 ⁇ 5'yH2 ⁇ are preferred.
- the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 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 are delayed release and have secondary washing properties.
- the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
- the term “amorphous” is also understood to mean “X-ray amorphous”.
- silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
- it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the above-mentioned organic builder substances can of course also be contained in the base granules, at least in part.
- bleaching agents are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate. Possible bleach activators and bleach catalysts have already been described in detail above.
- Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; in particular who ⁇ the alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, used.
- the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
- the content of normal sodium silicate (water glass) in the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
- Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
- Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
- cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the Means used.
- the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.
- Mixtures of the aforementioned brighteners can also be used.
- the basic granules can be produced by any of the known processes such as spray drying, granulation, compacting (roller compacting, pelleting, extrusion).
- the washing or cleaning agents according to the invention preferably do not contain any base granules which have been produced by spray drying.
- the washing or cleaning agent consists of a base granulate and an admixed additive according to the invention.
- granulators which can consist of mixers with mixing tools rotating in a housing, although other technical designs of granulators are also possible and conceivable.
- a method of this type is described, for example, in WO 93/23523 A1.
- the base granules can also be produced by extrusion of a premix with subsequent shaping, as is described in more detail, for example, in WO-A-91/02047.
- almost spherical base granules in particular extruded base granules, are mixed with almost spherical, rounded or rounded additives to form a heavy granular detergent or cleaning agent with bulk densities of preferably above 700 g / l.
- the (comparative) agent 1 had a bulk density of about 750 g / l.
- the sieve analysis (sieves 0.8 mm and 0.4 mm) showed that 74% by weight lay on the sieve 0.8 mm and 26% by weight lay on the sieve 0.4 mm. In the base extrudate used, the fraction on the 0.4 mm sieve was only 10% by weight; by mixing these finer parts were more than doubled!
- Example 2 the admixed components a) to e) were used to produce an additive in a mixer / granulator, the polymer being used not as a solid but as a granulating liquid in the form of a 30% by weight solution of Sokalan CP5®.
- the additive was then dried and had the following components and properties after drying:
- Agent 2 according to the invention had only a negligible reduction in the bulk density to 740 g / l to about 750 g / l.
- the sieve analysis (sieves 0.8 mm and 0.4 mm) showed that 85% by weight lay on the sieve 0.8 mm and only 15% by weight lay on the sieve 0.4 mm.
- the fraction on the 0.4 mm sieve was again 10% by weight; the granulation reduced the finer proportions compared to agent 1, and accordingly the aesthetics of the product were considerably improved.
- Agent 2 according to the invention also had a higher degree of whiteness (measured according to Berger and Ganz) than the (comparative) agent 1.
- agent 2 according to the invention also had an improved dissolving rate after 1.5 minutes compared to the dissolving rate of (comparison -) Using 1.
- Agent 2 according to the invention also showed significantly less segregation than (comparative) agent 1. This was investigated as follows: 3 filled 1.5 kg packages were emptied with measuring spoons, each sample being 100 g. Of the 15 samples in each package, every third sample was analyzed for anionic surfactant content (AT), perborate monohydrate content (PBMH) and bleach activator content (TAED). The values obtained (indicated in each case in% by weight) clearly show that by using the additive according to the invention it was possible to achieve a substantially better homogeneity in the package.
- AT anionic surfactant content
- PBMH perborate monohydrate content
- TAED bleach activator content
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1996127427 DE19627427A1 (de) | 1996-07-08 | 1996-07-08 | Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung |
DE19627427 | 1996-07-08 | ||
DE19632284 | 1996-08-09 | ||
DE1996132284 DE19632284A1 (de) | 1996-08-09 | 1996-08-09 | Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung |
PCT/EP1997/003468 WO1998001531A2 (de) | 1996-07-08 | 1997-07-02 | Wasch- oder reinigungsmitteladditiv sowie ein verfahren zu seiner herstellung |
Publications (3)
Publication Number | Publication Date |
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EP0888450A2 true EP0888450A2 (de) | 1999-01-07 |
EP0888450B1 EP0888450B1 (de) | 2000-05-24 |
EP0888450B2 EP0888450B2 (de) | 2003-01-15 |
Family
ID=26027305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP97933648A Expired - Lifetime EP0888450B2 (de) | 1996-07-08 | 1997-07-02 | Wasch- oder reinigungsmitteladditiv sowie ein verfahren zu seiner herstellung |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0888450B2 (de) |
JP (1) | JPH11513074A (de) |
AT (1) | ATE193322T1 (de) |
DE (1) | DE59701763D1 (de) |
ES (1) | ES2148999T5 (de) |
WO (1) | WO1998001531A2 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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AU2003231107A1 (en) | 2002-05-02 | 2003-11-17 | The Procter And Gamble Company | Detergent compositions and components thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4486327A (en) † | 1983-12-22 | 1984-12-04 | The Procter & Gamble Company | Bodies containing stabilized bleach activators |
DE3400008A1 (de) † | 1984-01-02 | 1985-07-11 | Henkel KGaA, 4000 Düsseldorf | Zur verwendung in tensidhaltigen mitteln geeignetes schaumregulierungsmittel |
GB8619634D0 (en) † | 1986-08-12 | 1986-09-24 | Unilever Plc | Antifoam ingredient |
US5002691A (en) † | 1986-11-06 | 1991-03-26 | The Clorox Company | Oxidant detergent containing stable bleach activator granules |
GB8811447D0 (en) * | 1988-05-13 | 1988-06-15 | Procter & Gamble | Granular laundry compositions |
GB8811954D0 (en) † | 1988-05-20 | 1988-06-22 | Unilever Plc | Antifoam ingredients |
US4997590A (en) † | 1988-12-22 | 1991-03-05 | The Procter & Gamble Company | Process of coloring stabilized bleach activator extrudates |
DE4024759A1 (de) † | 1990-08-03 | 1992-02-06 | Henkel Kgaa | Bleichaktivatoren in granulatform |
ES2084829T3 (es) † | 1990-09-28 | 1996-05-16 | Procter & Gamble | Detergente que contiene tensioactivos de alquil-sulfato y amida de acido graso polihidroxilado. |
DE4127323A1 (de) * | 1991-08-20 | 1993-02-25 | Henkel Kgaa | Verfahren zur herstellung von tensidgranulaten |
US5516449A (en) † | 1992-04-03 | 1996-05-14 | The Procter & Gamble Company | Detergent compositions |
DE4221736A1 (de) * | 1992-07-02 | 1994-01-05 | Henkel Kgaa | Feste waschaktive Zubereitung mit verbessertem Einspülverhalten |
CA2141587A1 (en) * | 1992-08-01 | 1994-02-17 | Anthony Dovey | Low gelling detergent compositions and a process for making such compositions |
ES2109720T3 (es) * | 1993-08-02 | 1998-01-16 | Henkel Kgaa | Granulado regulador de la espuma y procedimiento para su fabricacion. |
EP0639639B2 (de) † | 1993-08-17 | 2010-07-28 | The Procter & Gamble Company | Percarbonat-Bleichmittel enthaltende Waschmittelzusammensetzungen |
EP0639638A1 (de) † | 1993-08-18 | 1995-02-22 | The Procter & Gamble Company | Verfahren zur Herstellung von Reinigungsmittelzusammensetzungen |
DE19521365A1 (de) * | 1995-06-12 | 1996-12-19 | Henkel Kgaa | Feste und hochverdichtete waschaktive Zubereitungen mit verbesserter Löslichkeit auch schon bei niederen Flottentemperaturen |
EP0771864A1 (de) † | 1995-11-03 | 1997-05-07 | The Procter & Gamble Company | Granularer Entschäumer |
-
1997
- 1997-07-02 DE DE59701763T patent/DE59701763D1/de not_active Expired - Fee Related
- 1997-07-02 JP JP10504746A patent/JPH11513074A/ja not_active Ceased
- 1997-07-02 EP EP97933648A patent/EP0888450B2/de not_active Expired - Lifetime
- 1997-07-02 ES ES97933648T patent/ES2148999T5/es not_active Expired - Lifetime
- 1997-07-02 AT AT97933648T patent/ATE193322T1/de not_active IP Right Cessation
- 1997-07-02 WO PCT/EP1997/003468 patent/WO1998001531A2/de active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO9801531A3 * |
Also Published As
Publication number | Publication date |
---|---|
EP0888450B1 (de) | 2000-05-24 |
JPH11513074A (ja) | 1999-11-09 |
ES2148999T3 (es) | 2000-10-16 |
EP0888450B2 (de) | 2003-01-15 |
DE59701763D1 (de) | 2000-06-29 |
ES2148999T5 (es) | 2003-05-01 |
WO1998001531A2 (de) | 1998-01-15 |
ATE193322T1 (de) | 2000-06-15 |
WO1998001531A3 (de) | 1998-04-09 |
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