WO2005123893A1 - Gezielte granulation durch neutralisation im compomix - Google Patents
Gezielte granulation durch neutralisation im compomix Download PDFInfo
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- WO2005123893A1 WO2005123893A1 PCT/EP2004/006464 EP2004006464W WO2005123893A1 WO 2005123893 A1 WO2005123893 A1 WO 2005123893A1 EP 2004006464 W EP2004006464 W EP 2004006464W WO 2005123893 A1 WO2005123893 A1 WO 2005123893A1
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- Prior art keywords
- acid
- weight
- acids
- anionic surfactant
- mixer
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- 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 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
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- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 description 1
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- 235000019831 pentapotassium triphosphate Nutrition 0.000 description 1
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CNVZJPUDSLNTQU-OUKQBFOZSA-N petroselaidic acid Chemical compound CCCCCCCCCCC\C=C\CCCCC(O)=O CNVZJPUDSLNTQU-OUKQBFOZSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 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 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 235000019833 protease Nutrition 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000006337 proteolytic cleavage Effects 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 239000010670 sage oil Substances 0.000 description 1
- 239000010671 sandalwood oil Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- RYMZZMVNJRMUDD-HGQWONQESA-N simvastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)C(C)(C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 RYMZZMVNJRMUDD-HGQWONQESA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 230000009897 systematic effect Effects 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
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- CBYCSRICVDBHMZ-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCCCC(O)=O CBYCSRICVDBHMZ-UHFFFAOYSA-N 0.000 description 1
- ZTUXEFFFLOVXQE-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCC(O)=O ZTUXEFFFLOVXQE-UHFFFAOYSA-N 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 108010031354 thermitase Proteins 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 238000012250 transgenic expression Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZKWDCFPLNQTHSH-UHFFFAOYSA-N tribromoisocyanuric acid Chemical compound BrN1C(=O)N(Br)C(=O)N(Br)C1=O ZKWDCFPLNQTHSH-UHFFFAOYSA-N 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 108010068608 xanthan lyase Proteins 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 108010083879 xyloglucan endo(1-4)-beta-D-glucanase Proteins 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
Definitions
- the present invention relates to a method for producing surfactant granules. It relates in particular to a method which allows the bulk density of the surfactant granules and the distribution of the grain sizes to be set in a targeted manner.
- Surfactant granules are used for the production of solid detergents or cleaning agents, which e.g. available as powder or compact.
- Surfactant granules are produced, for example, by reacting anionic surfactant acids with neutralizing agents. This neutralization can be carried out both with solutions of alkali metal hydroxides and within a dry neutralization with solid alkaline substances, in particular sodium carbonate.
- the surfactant salts are obtained in the form of aqueous preparation forms, water contents being adjustable in the range from about 10 to 80% by weight and in particular in the range from about 35 to 60% by weight.
- Products of this type have a paste-like to cutable quality at room temperature, the flowability and pumpability of such pastes being restricted or even being lost in the range of approximately 50% by weight of active substance, so that such pastes are further processed, in particular when incorporated into them Solid mixtures, for example in solid washing and cleaning agents, considerable problems arise. Accordingly, it is an old need to be able to provide anionic detergent surfactants in dry, in particular free-flowing, form.
- European patent application EP-A-0 678 573 (Procter & Gamble) describes a process for producing free-flowing surfactant granules with bulk densities above 600 g / 1, in which anionic surfactant acids with an excess of neutralizing agent form a paste with at least 40% by weight of surfactant are reacted and this paste is mixed with one or more powder (s), at least one of which must be spray-dried and which contains anionic polymer and cationic surfactant, the resulting granules optionally being able to be dried.
- this document reduces the proportion of spray-dried granules in the detergents and cleaning agents, it does not completely avoid spray drying.
- European patent application EP-A-0 438 320 discloses a batch process for the production of surfactant granules with bulk densities above 650 g / l.
- Anionic surfactant acid is added to a solution of an alkaline inorganic substance in water, possibly with the addition of other solids, and granulated in a high-speed mixer / granulator with a liquid binder. Neutralization and granulation take place in the same apparatus, but in separate process steps, so that the process can only be operated in batches.
- ABS acid contains at least 62% NaOH is neutralized and then granulated with the addition of auxiliaries, for example ethoxylated alcohols or alkylphenols or a polyethylene glycol melting above 48.9 ° C. with a molecular weight between 4000 and 50,000.
- auxiliaries for example ethoxylated alcohols or alkylphenols or a polyethylene glycol melting above 48.9 ° C. with a molecular weight between 4000 and 50,000.
- EP-A-0 508 543 (Procter & Gamble) mentions a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40% by weight surfactant paste, which is then conditioned and granulated, one Direct cooling with dry ice or liquid nitrogen takes place.
- the liquid surfactant mixtures disclosed in this document contain sodium or potassium salts of alkylbenzenesulfonic acids or alkylsulfuric acids in amounts of up to 80% by weight, ethoxylated nonionic surfactants in amounts of up to 80% by weight and a maximum of 10% by weight of water.
- the surfactant mixtures to be sprayed on contain between 40 and 92% by weight of a surfactant mixture and more than 8 to a maximum of 60% by weight of water.
- the surfactant mixture in turn consists of at least 50% polyalkoxylated nonionic surfactants and ionic surfactants.
- a method for producing a liquid surfactant mixture from the three components anionic surfactant, nonionic surfactant and water is described in EP 507 402 (Unilever).
- the surfactant mixtures disclosed here, which are said to contain little water, are prepared by combining equimolar amounts of neutralizing agent and anionic surfactant acid in the presence of nonionic surfactant.
- German laid-open specification DE-A-42 32 874 discloses a process for the preparation of washable and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their acid form.
- Solid, powdery substances, in particular sodium carbonate are disclosed as neutralizing agents, which react with the anionic surfactant acids to form anionic surfactant, carbon dioxide and water.
- the granules obtained have surfactant contents of around 30% by weight and bulk densities of less than 550 g / l.
- the European patent application EP 642 576 (Henkel KGaA) describes a two-stage granulation in two consecutive mixers / granulators, one in first, low-speed granulator 40-100% by weight, based on the total amount of the constituents used, of the solid and liquid constituents, and in a second, high-speed granulator, the pre-granules are mixed with the remaining constituents, if necessary, and converted into granules.
- German Offenlegungsschrift DE-A-43 14 885 discloses a process for producing washable and cleaning-active anionic surfactant granules by neutralizing the acid form of anionic surfactants with a compound having a basic action, the hydrolysis-sensitive acid form of a hydrolysis-sensitive anionic surfactant containing the neutralizing agent without the release of Water is implemented.
- Sodium carbonate is preferably used as the neutralizing agent, which reacts to sodium hydrogen carbonate in this process.
- the object of the present invention was to provide a continuous or discontinuous process for the production of surfactant granules by neutralizing anionic surfactant acids and solid neutralizing agents.
- the bulk densities of the granules to be produced should be selectively adjustable within wide limits, and it was a particular object of the present invention to be able to achieve the low bulk densities of conventional spray drying products using a non-tower process. Furthermore, it should be possible to influence the grain size distribution of the granules by varying suitable factors. By means of a targeted procedure, it should in particular be made possible that the end products are superior to the products that can be produced by prior art processes.
- the end products should have a high solubility, which is a prerequisite for the quick and complete dissolution of the detergent or cleaning agent portion, especially when used in the form of compact. Furthermore, the granules are expected to optimize their shelf life. In the case of a longer storage period, the individual granules should not stick together, nor should the different granule sizes be inhomogeneously distributed in one quantity of granules due to a broad grain size distribution.
- the present invention relates to a process for the production of surfactant granules with a bulk density of 300 to 800 g / 1 by neutralizing anionic surfactant acids and optionally further acidic components with solid neutralizing agents, in which the anionic surfactant acid (s) and the solid neutralizing agent (s) agglomerated in a free-fall mixer and, if necessary, subsequently processed, characterized in that the anionic surfactant acid has a water content of between 5 and 24% by weight.
- anionic surfactant acids are reacted with solid neutralizing agents.
- Suitable anionic surfactant acids for this process are in principle all anionic surfactant acids known to those skilled in the art.
- one or more substance (s) from the group of the carboxylic acids, the sulfuric acid half-esters and the sulfonic acids preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylarylsulfonic acids, in particular from the group, are used as anionic surfactant acid (s) the C 8 - 16 -. especially the C 9 . 13- Alkylbenzenesulfonic acids used. These are described below.
- the compounds mentioned should have longer-chain hydrocarbon radicals, that is to say they should have at least 6 carbon atoms in the alkyl or alkenyl radical.
- the C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.
- Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaning agents, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Processes used on an industrial scale are, for example, fission in an autoclave or continuous high pressure splitting.
- Carboxylic acids which can be used as an anionic surfactant in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc.
- fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotinic acid), triacidic acid (melotonic acid), and melonic acid unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidinic acid), 9c, 12c-oc
- Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C 8, 6 wt .-% C 10 48 wt .-% C 12 18 wt .-% C14, 10 wt .-% C 16, 2 wt .-% C 18 , 8 wt .-% C 18 -, 1 wt .-% C 18 -), pal nuclear oil fatty acid (approx. 4 wt .-% C 8 , 5 wt .-% C 1 0, 50 wt.
- Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the process according to the invention.
- Their alkali metal, in particular sodium salts, the fatty alcohol sulfates are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized.
- the fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters.
- the most important industrial process for the production of Fatty alkyl sulfuric acids is the sulfonation of alcohols with SOs / air mixtures in special cascade, falling film or tube bundle reactors.
- alkyl ether sulfuric acids which can be used in the process according to the invention are the alkyl ether sulfuric acids, the salts of which, the alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
- alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the alkyl ether sulfuric acids concerned.
- Alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention.
- Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the carbon chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons.
- n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which, in the case of hydrolysis with alkalis, give the alkanesulfonates directly and, when reacted with water, the alkanesulfonic acids.
- di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.
- alkanesulfonic acids Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under irradiation with UV light.
- This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals.
- the reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical.
- the reaction of the two radicals with unreacted paraffin gives the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to give sulfuric acid.
- this reaction is usually only carried out up to degrees of conversion of 1% and then stopped.
- Olefin sulfonates are produced industrially by the reaction of ⁇ -olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize into so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids.
- alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with aluminum and neutralized with sodium hydroxide solution.
- propylene was tetramerized to give branched ⁇ -dodecylene and the product was converted to tetrapropylene benzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized.
- TPS tetrapropylene benzene sulfonates
- Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins.
- petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrated to the n-olefins, resulting in both ⁇ - and / -olefins.
- the resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed:
- the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, on the other hand, becomes hydrogen fluoride as a catalyst used, the content of 2-phenyl isomer can be reduced to approximately 20% by weight.
- the sum of x and y is usually between 5 and 13.
- the method according to the invention in which the anionic surfactant in acid form of C 8- ⁇ 6 -, preferably C 9-13 - alkyl benzenesulfonic acids are used, are preferred. It is within the scope of the present invention further preferably, C 8- ⁇ 6 -, preferably C. 9 13 - to use alkylbenzenesulfonic acids which are derived from alkylbenzenes and which have a tetralin content below 5% by weight, based on the alkylbenzene.
- alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C 8 . 16 -, preferably C 9-13 - alkylbenzenesulfonic acids have a 2-phenyl isomer content below 22% by weight, based on the alkylbenzenesulfonic acid.
- anionic surfactants in their acid form can be used alone or in a mixture with one another in the process according to the invention.
- the anionic surfactant in acid form, before addition to the solid neutralizing agent (s) contains further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably from 1 to 15% by weight and in particular from 2 to 10% by weight, based in each case on the weight of the mixture containing anionic surfactant acid.
- Suitable acidic reactants in the context of the present invention are, in addition to the "surfactant acids", the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids as well as “builder acids” and “complex builder acids” alone or in any mixtures.
- the main ingredients of detergents and cleaning agents that can be mixed with anionic surfactant acid are acid detergent and cleaning agent ingredients, e.g. phosphonic acids, which are neutralized form (phosphonates) as incrustation inhibitors and a component of many detergents and cleaning agents.
- the use of (partially neutralized) polymer acids such as polyacrylic acids is also possible.
- acid-stable ingredients with the anionic surfactant acid.
- so-called small components are available which would otherwise have to be added in complex further steps, for example optical brighteners, dyes, etc., the acid stability being checked in individual cases.
- Nonionic surfactants are preferred for the anionic surfactant in acid form in amounts of 0.1 to 40% by weight, preferably 1 to 15% by weight and in particular 2 to 10% by weight, in each case based on the weight of the anionic surfactant-containing Mixture, mixed. This addition can improve the physical properties of the mixture containing anionic surfactant acid and make subsequent incorporation of nonionic surfactants into the surfactant granules or the entire detergent and cleaning agent unnecessary.
- the different representatives from the group of nonionic surfactants are described below.
- the anionic surfactant acids converted in the process according to the invention have a water content of between 5 and 24% by weight.
- anionic surfactant acids which contain 5 to 24% by weight of water are used in the process described.
- less than 5% by weight of water, based on the neutralizing agent is preferably introduced into the mixer by the neutralizing agent.
- a water content of less than 4% by weight, in particular less than 3% by weight, in the neutralizing agent is particularly preferred.
- the neutralizing agent contains 1-2% by weight of water.
- Such a process differs from typical processes of the prior art, in which water enters the reaction mixture through the use of water-containing neutralizing agents, such as aqueous neutralizing agent pastes or aqueous solutions of neutralizing agents.
- water-containing neutralizing agents such as aqueous neutralizing agent pastes or aqueous solutions of neutralizing agents.
- anionic surfactant acids contain up to 3% by weight of water.
- both the bulk weights and the particle size distribution of the process products can be set in a targeted manner by the process according to the invention.
- the anionic surfactant acid contains 5-17% by weight of water. Water contents of the acid which are between 6 and 16% by weight, particularly preferably between 7 and 15% by weight and in particular between 8 and 14% by weight are preferred for this embodiment.
- the bulk densities are preferably 300-600 g / l, particularly preferably 400-600 g / l, in particular 500-600 g / l.
- the proportion of the surfactant granules which have a grain size between 100 and 800 ⁇ m before the preparation is at least 40% by weight, preferably at least 47% by weight, particularly preferably at least 55% by weight, very particularly preferably at least 60% by weight and in particular at least 70% by weight.
- the proportion of coarse-grained granules with grain sizes between 800 and 1600 ⁇ m is preferably more than 20% by weight, particularly preferably more than 25% by weight, in particular more than 30% by weight, before processing.
- the proportion of fine-grained granules with grain sizes between 100 and 200 ⁇ m is preferably less than 17% by weight, particularly preferably less than 14% by weight, in particular between 1 and 12% by weight.
- the preferred object of the invention is a process for the production of surfactant granules with a bulk density of 300 to 600 g / l by neutralization of anionic surfactant acids and optionally further acidic components with solid Neutralizing agents in which the anionic surfactant acid (s) and the solid neutralizing agent (s) are agglomerated in a free-fall mixer and, if necessary, subsequently processed, characterized in that the anionic surfactant acid has a water content of between 5 and 17% by weight.
- the anionic surfactant acid contains 10-24% by weight of water. Water contents of the acid which are between 11 and 23% by weight, particularly preferably between 12 and 22% by weight and in particular between 13 and 21% by weight are preferred for this embodiment.
- a form of the process according to the invention in which the water content of the anionic surfactant acid is between 14 and 20% by weight and in particular between 15 and 19% by weight is very particularly preferred.
- the water content of the anionic surfactant acid is selected from the range between 10 and 24% by weight described in the previous section, granules with medium bulk densities are obtained after the neutralization / granulation.
- the bulk weights are preferably 500-800 g / l, particularly preferably 500-700 g / l, in particular 500-600 g / l.
- the proportion of the surfactant granules which have a grain size between 100 and 800 ⁇ m before the preparation is at least 52% by weight, preferably at least 62% by weight, particularly preferably at least 70% by weight, very particularly preferably at least 76% by weight and in particular at least 80% by weight.
- the proportion of the coarse-grained granules with grain sizes between 800 and 1600 ⁇ m before processing is less than 20% by weight, particularly preferably less than 15% by weight, in particular between 1 and 10% by weight.
- the proportion of fine-grained granules with grain sizes between 100 and 200 ⁇ m is preferably greater than 17% by weight, particularly preferably greater than 23% by weight, in particular greater than 27% by weight.
- the preferred object of the invention is a process for the production of surfactant granules with a bulk density of 500 to 800 g / l by neutralizing anionic surfactant acids and optionally further acidic components with solid neutralizing agents, in which the anionic surfactant acid (s) and the solid neutralizing agent (s) agglomerated in a free-fall mixer and, if necessary, subsequently processed, characterized in that the anionic surfactant acid has a water content of between 10 and 24% by weight.
- the neutralized form of the anionic surfactant acids in short the anionic surfactants, can be present in varying amounts in the agents produced by the process according to the invention.
- Preferred processes according to the invention are characterized in that the neutralized anionic surfactant acid content of the process products is at most 80% by weight, preferably 8 to 72% by weight, particularly preferably 10 to 65% by weight and in particular 15 to 55% by weight is.
- the process according to the invention is therefore suitable for the production of surfactant-rich granules with a surfactant content greater than 40% by weight as well as for the production of comparatively low surfactant granules.
- the surfactant-rich process products preferably contain neutralized anionic surfactant acids in proportions by weight of 40 to 80% by weight, preferably 45 to 75% by weight, particularly preferably 50 to 72% by weight and in particular 60 to 70% by weight. These process products are preferably used in washing and cleaning agent concentrates.
- low-surfactant process products are obtained in which neutralized anionic surfactant acids in a proportion by weight of at most 50% by weight, preferably between 8 and 42% by weight, particularly preferably between 10 and 35% by weight and in particular between 20 and 30 wt .-% are included.
- These process products are mainly used in the production of high-volume standard washing and cleaning agents.
- neutralizing agents known to the person skilled in the art are suitable as solid neutralizing agents for this process.
- one or more substances of the compounds sodium carbonate, sodium hydroxide, sodium sesquicarbonate, potassium hydroxide and / or potassium carbonate are used as neutralizing agents.
- components not participating in the reaction can also be added to the neutralizing agent. These should then have sufficient stability with respect to the added acids in order to avoid local decomposition and thus undesirable discoloration or other stress on the product.
- Processes are preferred here in which further solids from the groups of the silicates, aluminum silicates, sulfates, citrates and / or phosphates are used.
- sodium sulfate which is still contained in the detergents in some countries up to 45% by weight, be added to the solid neutralizing agent (s).
- the weight ratio of the solid neutralizing agent (s) used in the process according to the invention can vary within wide limits.
- Processes according to the invention are preferred here in which the weight ratio of the solid neutralizing agent (s) used in the process according to the invention to the anionic surfactant acid (s) used and, if appropriate, further acidic components between 100: 1 and 1: 5, preferably between 80: 1 and 1: 4, preferably between 60: 1 and 1: 3, very particularly preferably between 40: 1 and 1: 2 and in particular between 20: 1 and 1: 1.
- the neutralizing agent to be used preferably contains less than 5% by weight of free water.
- the neutralizing agent contains less than 2% by weight of free water.
- the neutralizing agent described in the section above is mixed in a free-fall mixer with anionic surfactant acid containing 5 to 24% by weight of water.
- the choice of the weight ratio between neutralizing agent and water influences the storage stability and the solution behavior as well as the bulk density of the granules and the distribution of the grain sizes.
- the weight ratio of the solid neutralizing agent used to the water introduced with the anionic surfactant acid is between 800: 1 and 2: 3.
- a ratio of the proportionate weights between 199: 1 and 1: 1, in particular between 99: 1 and 15: 7, is preferred.
- the ratio of the proportionate weights of neutralizing agent and water is between 19: 1 and 19: 6.
- the water content of the end products of the process, determined by loss of drying at 120 ° C. is preferably less than 26% by weight, preferably 1-15% by weight, particularly preferably 1-10% by weight and in particular 4-5% by weight.
- the process according to the invention is characterized by the use of free-fall mixers for carrying out the neutralization of anionic surfactant acids with solid neutralizing agents.
- the free fall mixers can be operated continuously or discontinuously.
- free-fall mixers are those mixers in which the mix is taken up by wall friction and then falls freely through the mixer space due to its own gravity.
- Free-fall mixers of this type have a movable or rotating reactor housing or a moving mixing vessel.
- Suitable containers are those with simple geometric shapes (cylinders, single or double cones, cubes, etc.).
- Preferred mixing containers also have inner corners which are as obtuse as possible, since this facilitates both the free movement of the mixing material and the emptying and cleaning of the container after the end of the process. The movement of the container must be transferred to the mix inside, so that the reaction mixture is thrown and loosened as irregularly as possible.
- the solid neutralizing agent moved in the free-fall mixer forms a falling powder curtain, onto which the anionic surfactant acids are sprayed.
- Rotation about a container axis drum or rotary tube mixer
- axes that do not match the geometric axes of the container or are perpendicular to its symmetry planes tumble mixer
- vibrate preferably with, are particularly suitable as types of movement for the free-fall mixer high amplitude and low frequency as well as changing directions of the deflections, so that irregularly shaking or tumbling movements occur.
- a directional movement component must occur in order to ensure the continuous mass transport and thus to enable a continuous method. To the same extent, a discontinuous process is preferred, with a directional movement component not being desired.
- Free-fall mixers which rotate about their horizontal axis, preferably about their slightly inclined axis, are particularly suitable for continuous operation. Due to the inclination of the axis of rotation, the mix has a directional movement due to its own gravity, which enables the mix to be continuously discharged from the mixer. In addition to the inclination of the axis of rotation, such a directional movement can of course also be produced by a continuous introduction of anionic surfactant acids and solid neutralizing agent. For the product properties, in particular for the adjustment of the bulk density and the solubility of the reaction products, it has proven to be advantageous if the angle of inclination of the axis of rotation of a preferably used rotatable container correlates with a certain number of revolutions.
- Methods according to the invention are therefore particularly preferred in which the rotatable container of the free-fall mixer has an inclination angle ⁇ of 0 to 20 °, in particular 0 to 15 °, very particularly preferably 1 to 15 °, and the movement of the rotatable container of the free-fall mixer is controlled by the drive is simultaneously set to 20 to 70 revolutions per minute and in particular to 30 to 60 revolutions per minute.
- Free-fall mixers preferred in the context of the present invention are drum mixers, tumble mixers, cone mixers, double cone mixers or V-mixers.
- the free-fall mixers used according to the invention offer alternating, inclined walls to the material carried up and falling again in the case of rotating or tumbling movements and thus deflecting, expanding or narrowing the space, shifting and dividing the flow of material.
- Such reactors can also have static and / or movable mixing and / or cutting tools. However, preference is given to rotating reactors in which the mix is taken up by wall friction and then falls freely through the mixer space due to its own gravity.
- Methods according to the invention are particularly preferred in which double-cone mixers with a rotatable container without mixing tools are used as free-fall mixers, the continuously operated double-cone mixers being subdivided into a mixing zone and a post-mixing zone and having a knock-off bar attached to an end plate is fixed and from there crosses the entire mixing zone and, if necessary, extends into the post-mixing zone.
- the ratio of the length of the mixing zone to the length of the post-mixing zone is preferably at least 1: 1.
- the tee can have a width of 50 to 150 mm, preferably 75 to 130 mm.
- the upper edge of the knock-off bar is at a distance from the inner mixer wall which is preferably a maximum of 10% of the drum diameter of the narrowest point of the rotatable container, preferably a maximum of 5% of the narrowest point of the rotatable container and in particular less than 2.5% of the narrowest point of the rotatable container Container.
- the distance to the nearest inner mixer wall can be greater than in the mixing zone; Values between 100 and 300 mm are quite common.
- the residence time of the reaction mixture in the free-fall mixer is preferably less than 20 minutes, preferably between 1 and 600 seconds, particularly preferably between 1 and 300 seconds and in particular between 1 and 120 seconds.
- the temperature of the mixture to be applied is as low as possible is.
- the liquid, acidic component has a temperature of 20 to 60 ° C., preferably 30 to 55 ° C. and in particular 40 to 50 ° C. when it is introduced into the free-fall mixer.
- the “liquid, acidic component” is the anionic surfactant acid, which comprises water and, if appropriate, further acidic components.
- the reaction between anionic surfactant acid (s) and sodium carbonate is carried out in such a way that the reaction Na 2 CO 3 + 2 anionic surfactant-H -> 2 anionic surfactant-Na + CO 2 + H 2 O
- the sodium carbonate is used in excess, so that unreacted sodium carbonate remains in the product, while sodium hydrogen carbonate is additionally formed in the reaction.
- the amount of sodium carbonate on average (based on the agent, without taking into account any hydrate water content that may be present) is related to the amount of sodium bicarbonate on average (based on the agent, without taking into account any hydrate water content that may be present).
- the mass ratio of sodium carbonate to sodium bicarbonate is within narrow limits, the weight ratio of sodium carbonate to sodium bicarbonate in the end products of the process being 50: 1 to 5: 1, preferably 40: 1 to 5.1: 1, in processes preferred according to the invention, particularly preferably 35: 1 to 5.2: 1 and in particular 30: 1 to 5.25: 1.
- Another way to promote the formation of sodium bicarbonate and to avoid the formation of carbon dioxide and water is to maintain the lowest possible temperatures. This can be achieved, for example, by cooling, but also by suitable process control or by coordinating the amounts of the reactants. Processes according to the invention are preferred here in which the temperature during the process is kept below 100 ° C., preferably below 80 ° C., particularly preferably below 60 ° C. and in particular below 50 ° C.
- the content of sodium hydrogen carbonate in the end products of the process can vary.
- the content of sodium bicarbonate in the process end products is 0.01 to 20% by weight, preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight and in particular 1 to 10% by weight. -%, each based on the total weight of the process end products.
- the content of sodium hydrogen carbonate in the end products of the process is between 2 and 10% by weight, preferably between 2.5 and 10% by weight, particularly preferably between 3 and 10% by weight and in particular between 4 and 10% by weight.
- the granules can be post-treated if necessary.
- the surfactant granules are either discharged directly through the discharge after they have passed through the post-mixing zone, or are transported on via a conveyor device.
- the term "aftertreatment” includes in particular the spray granulation, that is to say the further addition of liquid binders, the encapsulation, the powdering with surface modifiers, the exposure to nonionic surfactants, the drying or the spray drying, the cooling and the separation of coarse and / or fine fractions summarized.
- Amorphous and / or crystalline aluminosilicates such as zeolite A, X and / or P, various types of silicas, calcium stearate, carbonates, sulfates, but also finely divided compounds, for example of amorphous silicates and carbonates, are preferred.
- Preferred nonionic surfactants are 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 per mole of alcohol, alkyl glycosides of the general formula RO (G) x , alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, amine oxides and
- Hot air is preferably used for drying.
- the cooling is preferably carried out by
- Post-treatment naturally also includes the "post-ripening" of a product, for example the termination of the chemical reaction when neutralization reactions are carried out.
- the aftertreatment comprises spray granulation and / or encapsulation and / or powdering with surface modifiers and / or exposure to nonionic surfactants and / or drying and / or spray drying onto inert bodies and / or cooling and / or a separation of coarse and / or fine fractions.
- the aftertreatment of the process products after discharge from the free-fall mixer on a reaction zone is a characteristic of particularly preferred embodiments of the present method according to the invention, whereby again those method variants are very particularly preferred in which the reaction zone is a pneumatic fluidized bed and / or a conveyor belt and / or is a mixer. If this conveyor and metering screw extends into the post-mixing zone (it is also possible to connect the conveyor directly to the discharge unit), it is preferred that the screw only protrude at most into the second length half of the post-mixing zone and therefore not into the part of the post-mixing zone , which still contains the tee.
- the residence time in the post-mixing zone is preferably between 1 and 19 minutes, preferably between 2 and 17 minutes, very particularly preferably between 3 and 14 minutes, in particular between 3 and 10 minutes.
- the agents produced by the process according to the invention can have different bulk densities depending on the content of the individual ingredients, in particular the water, and other process parameters.
- Preferred embodiments of the process according to the invention are those in which the bulk density of the end products of the process is 300 to 800 g / l, preferably 350 to 700 g / l, particularly preferably 400 to 650 g / l and in particular 500 to 600 g / l.
- the granules obtained have an increased solubility in water / aqueous solutions and an increased shelf life compared to the granules described in the prior art. Both the gluing of individual granules and the Demixing of a quantity of granules after movement (tilting / shaking) of the storage container was not observed.
- These process products also have a particle size distribution with an average particle size d 50 below 5000 ⁇ m, preferably between 20 and 3000 ⁇ m, particularly preferably between 40 and 2000 ⁇ m and in particular between 50 and 1600 ⁇ m.
- the surfactant granules with a grain size between 100 and 1600 ⁇ m preferably have a weight fraction of at least 80 wt.%, Preferably at least 82 wt.%, Particularly preferably at least 85 wt.%, Very particularly preferably at least 90 wt. % and in particular at least 95% by weight.
- surfactant granules which have a grain size between 100 and 800 ⁇ m before the preparation are very particularly preferred in parts by weight of at least 52% by weight, preferably at least 62% by weight, particularly preferably at least 70% by weight preferably at least 76% by weight and in particular at least 80% by weight.
- the surfactant granules produced by the process according to the invention are particularly suitable for producing detergents or cleaning agents, in particular solid detergents or cleaning agents, for example by further agglomeration, by extrusion or compacting.
- Such detergents or cleaning agents contain, in addition to the ingredients mentioned above, such as the anionic surfactant acids, further constituents, in particular from the group of builders, cobuilders, bleaching agents, bleach activators, dyes and fragrances, optical brighteners, enzymes, soil-release polymers, etc. These substances are described below for completeness.
- Builders are mainly used in detergents or cleaning agents to bind calcium and magnesium.
- Usual builders which in the context of the invention are preferably present in amounts of 22.5 to 45% by weight, preferably 25 to 40% by weight and in particular 27.5 to 35% by weight, in each case based on the total composition , which also contains the end products of the process according to the invention, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates. Trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of alkali disilicates are preferably used for washing or cleaning agents.
- the potassium salts are preferable to the sodium salts, since they often have a higher solubility in water.
- Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
- Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean 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, aminocarboxylic acids, nitrilothacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
- the acids themselves can also be used.
- the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergents or cleaning agents.
- Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
- Polymeric polycarboxylates are also suitable as builders or scale inhibitors; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
- the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
- GPC gel permeation chromatography
- the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
- the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
- 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 from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
- the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
- Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers , Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
- polymeric aminodicarboxylic acids their salts or their precursor substances.
- Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
- polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
- DE dextrose equivalent
- the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
- Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders.
- Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
- Glycine disuccinates and glycerol trisuccinates are also preferred in this connection. Suitable amounts used in formulations containing zeolite and / or silicate are from 3 to 15% by weight.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may 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.
- Washing or cleaning agents can contain phosphates as builders, preferably alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
- phosphates as builders, preferably alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
- Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
- the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits and also contribute to cleaning performance.
- the detergents or cleaning agents can particularly preferably contain condensed phosphates as water-softening substances. These substances form a group of phosphates - also called melting or glow phosphates due to their production - which can be derived from acid salts of orthophosphoric acid (phosphoric acids) by condensation.
- the condensed phosphates can be divided into the metaphosphates [M ' n (PO 3 ) n ] and polyphosphates (M l n +2 P n O 3n + 1 or M' n H 2 P n O 3n + ⁇ ).
- Metaphosphates are obtained as by-products of Graham 's salt, which is incorrectly referred to as sodium hexametaphosphate, by melting NaH 2 PO 4 at temperatures above 620 ° C, with what is known as Maddrell 's salt being formed as an intermediate.
- This and Kurrol 's salt are linear polyphosphates, which today are mostly not counted among the metaphosphates, but which can also be used with preference as water-softening substances in the context of the present invention.
- the quenched, glassy melt is the water-soluble Graham 's salt, (NaPO 3 ) 0 . 5 o, or a glassy condensed phosphate of the composition (NaPO 3 ) 15-20 known as Calgon.
- the misleading name hexametaphosphate is still used for both products.
- Kurrol 's salt (NaPO 3 ) n with n »5000, also arises from the melt of the Maddrell 's salt, which is hot at 600 ° C, if it is left at 500 ° C for a short time. It forms highly polymeric water-soluble fibers.
- the phosphonates represent a class of substances with cobuilder properties. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
- Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g.
- HEDP is preferably used as the builder from the class of the phosphonates.
- the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
- Suitable silicate builders are the crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 H 2 O, 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 are 2, 3 or 4.
- Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred.
- the delay in dissolution compared to conventional amorphous sodium silicates can be 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 provide 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 also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P are also suitable.
- Suitable zeolites have an average grain size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- acidifying agents In addition to the builders, acidifying agents, chelate complexing agents or deposit-inhibiting polymers are further preferred ingredients of detergents or cleaning agents.
- Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients.
- the solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
- the anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available.
- Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
- Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated connections are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.
- Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
- complex-forming polymers i.e. polymers that either carry themselves in the main chain or laterally to these functional groups, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes can be used.
- the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
- Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific activities towards ions of different metals.
- the base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.
- All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups.
- the following are preferably used individually or in a mixture: a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 3-nitridodiacetic acid, nitridodiacetic acid , N-di- ( ⁇ -hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilothacetic acid (NTA), c) geminal diphosphonic
- polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5.
- Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the required alkaline pH values of the treatment solutions, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
- Deposit-inhibiting polymers can also be contained in washing or cleaning agents. These substances, which can have a different chemical structure, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.
- Deposit-inhibiting polymers can also have cobuilder properties.
- organic cobuilders in the agents that the invention Process end products contain, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates are used. These classes of substances have been described above.
- bleaching agents which can be used are, for example, nathumper carbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- Preferred washing or cleaning agents can also contain bleaching agents from the group of organic bleaching agents.
- Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
- organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
- Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylactic acid, peroxystearic acid, ⁇ -phthalimidthanoic acid poperoxycaproic acid [ ], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidooper succinate and (c) peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassyl acid, the
- Diperoxyphthalic acids 2-decyldiperoxybutane-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid).
- Chlorine or bromine-releasing substances can also be used as bleaching agents.
- Suitable materials that release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
- DICA dichloroisocyanuric acid
- Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
- Bleach activators support the effects of the bleach.
- Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1, 5-diacetyl-2,2-dioxo-hexahydro-1, 3,5-triazine DADHT and isatoic anhydride ISA.
- Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
- acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran, n-methyl-
- TAED tetraacetylethylenediamine
- N-acylimides in particular N-nonanoylsuccinimide (NOSI)
- bleach catalysts can also be used in the secondary products of the process according to the invention be included.
- These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
- Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach catalyst can be used.
- Detergents or cleaning agents can contain enzymes to increase the washing or cleaning performance, although in principle all enzymes established in the prior art can be used for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Preferred agents preferably contain enzymes in total amounts of I x 10 ⁇ to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method.
- BCA method bicinchoninic acid
- subtilisins BPN subtilisins BPN "and Carlsberg
- subtilisins PB92 subtilisins 147 and 309
- the alkaline protease from Bacillus lentus subtilisin DY
- subtilisins 147 and 309 the alkaline protease from Bacillus lentus
- subtilisin DY the enzymes thermitase
- proteinase K the enzyme which can no longer be assigned to the subtilisins in the narrower sense
- Subtilisin Carlsberg is available in further developed form under the trade name Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark
- subtilisins 147 and 309 are sold under the trade names Esperase ® and Savinase ® from Novozymes From the protease Bacillus lentus DSM 5483 are derived from the variants known as BLAP ® .
- proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, which is sold under the trade name Protosol ® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ® and Protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
- amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus, and their further developments, which are improved for use in detergents and cleaning agents.
- the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST.
- Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
- the ⁇ -amylase from ß. Amyloliquefaciens is sold by Novozymes under the name BAN ® , and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ® , also from Novozymes.
- ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from ß. highlight agaradherens (DSM 9948); fusion products of the molecules mentioned can also be used.
- Washing or cleaning agents can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
- lipases or cutinases include, for example, those originally from Humicola lanuginosa (Thermomyces lanuginosus) available or further developed lipases, especially those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ® , Lipolase ® Ultra, LipoPrime ® , Lipozyme ® and Lipex ® .
- the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
- lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase ® , Lipase AP ® , Lipase M-AP ® and Lipase AML ® available.
- the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
- Detergents or cleaning agents can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
- These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a "stone washed" effect.
- EG endoglucanase
- Novozymes A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ® .
- the products Endolase ® and Carezyme ® also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800.
- Other possible commercial products from this company are Cellusoft ® and Renozyme ® .
- the 20 kD EG cellulase from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ® and Biotouch ® can also be used.
- Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA , The obtained from B. subtilis .beta.-glucanase is available under the name Cereflo ® from Novozymes.
- washing and cleaning agents can contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) , Suitable commercial products are Denilite ® 1 and 2 from Novozymes.
- organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) when the redox potentials between the oxidizing enzymes and the soiling differ greatly.
- the enzymes used in detergents or cleaning agents either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced according to known biotechnological processes by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
- the enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
- the enzymes can be added to detergents or cleaning agents in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.
- the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzyme is enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
- Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers.
- Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
- a protein and / or enzyme contained in a detergent or cleaning agent can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
- damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
- the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
- Stabilizers can preferably be used for this purpose.
- a group of stabilizers are reversible protease inhibitors.
- Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho, meta- or para-substituted phenylboronic acids, or their salts or esters.
- Peptide aldehydes, ie oligopeptides with a reduced C-terminus are also suitable. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
- Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End group-capped fatty acid amide alkoxylates can also be used as stabilizers.
- Di-glycine phosphate also protects against denaturation by physical influences.
- Calcium salts are also used, such as calcium acetate or calcium formate and magnesium salts.
- Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides, stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
- Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors.
- Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
- Alkyl polyglycosides can also stabilize the enzymatic components of the preferred agent and even increase their performance.
- Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.
- Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of the enzymes against oxidative breakdown.
- Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
- the action of peptide-aldehyde stabilizers can be increased by the combination with boric acid and / or boric acid derivatives and polyols and can be further enhanced by the additional use of divalent cations, such as calcium ions.
- the use of liquid enzyme formulations is particularly preferred in the context of the present invention.
- the additional enzymes and / or enzyme preparations preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably 1, 5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the total composition.
- Dyes and fragrances can be added to detergents or cleaning agents to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and distinctive" product in addition to performance.
- perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g.
- the ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
- the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethylionon and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.
- perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
- the fragrances can be incorporated directly into the compositions, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
- Cyclodextrins for example, have proven useful as such carrier materials, the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
- dyes In order to improve the aesthetic impression of the washing or cleaning agents, it (or parts thereof) can be colored with suitable dyes.
- Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to the substrates to be treated with the compositions, such as glass, ceramics or plastic dishes, so as not to stain them.
- Detergents or cleaning agents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
- brighteners of the substituted diphenylstyryl type may be present, e.g.
- the end products of the process according to the invention can not only be admixed with particulate detergents or cleaning agents, but can also be used in detergent or cleaning agent tablets. Surprisingly, the solubility of such tablets is improved by using the end products of the process according to the invention compared to tablets of the same hardness and of identical composition which do not contain any end products of the method according to the invention.
- Another object of the present invention is therefore the use of the process end products of the process according to the invention for the production of detergents, in particular detergent tablets.
- the washing and cleaning-active molded articles are produced by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
- the mixture to be tabletted is pressed directly, ie without prior granulation.
- the advantages of this so-called direct tableting are its simple and inexpensive use, since no further process steps and consequently no further plants are required.
- these advantages are offset by disadvantages.
- a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties. Furthermore, it must not show any tendency to segregate during storage, transport and filling of the die.
- the premix Before the particulate premix is pressed into detergent tablets, the premix can be finely divided
- Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used.
- the premix is preferably “powdered” with finely divided zeolite, faujasite-type zeolites being preferred.
- faujasite-type zeolite denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (compare Donald W.
- Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites which do not necessarily have to belong to structure group 4 of the zeolite can also be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent from a zeolite of faujasite -Type exist.
- detergent tablets consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 ⁇ m , preferably below 10 ⁇ m and in particular below 5 ⁇ m, and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be pressed.
- the premixes to be pressed can additionally include one or more substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and contain corrosion inhibitors. These substances have been described above.
- the molded articles are first produced by dry mixing the constituents, which can be wholly or partially pre-granulated, and then providing information, in particular pressing them into tablets, whereby conventional methods can be used.
- the premix is compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to below as tableting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
- the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
- the constant dosing, even at high molding throughputs, is preferably carried out via a volumetric dosage of the premix reached.
- the upper punch touches the premix and lowers further towards the lower punch.
- the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
- the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
- the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
- the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).
- Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
- eccentric tablet presses are preferably used, in which the punch or stamps are attached to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these stamps is comparable to the way a conventional four-stroke engine works.
- the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being correspondingly increased.
- the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
- rotary tablet presses are selected in which a larger number of matrices are arranged in a circle on a so-called die table.
- the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
- Each die on the die table is assigned an upper and lower stamp, with the pressing pressure again being active only through the upper and lower stamp, but can also be built using both stamps.
- the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
- these cam tracks are supported by additional low-pressure pieces, pull-down rails and lifting tracks.
- the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
- the press pressure on the premix can be individually adjusted via the press paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
- Rotary presses can also be equipped with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
- several filling shoes are arranged one behind the other without the lightly pressed first layer being ejected before further filling.
- jacket and dot tablets can be produced in this way, which have an onion-shell-like structure, in the case of the dot tablets the top of the core or the core layers is not covered and thus remains visible.
- Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
- the throughputs of modern rotary tablet presses are over one million tablets per hour.
- Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
- Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (Sl ).
- the hydraulic double-pressure press HPF 630 from LAEIS is particularly suitable.
- D. Tableting tools are, for example, from Adams Tablettierwerkmaschinen, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber & Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
- Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (Sl).
- the moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all usable configurations come into consideration as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side faces, and in particular cylindrical configurations with circular or oval shapes Cross-section.
- This last embodiment encompasses the form of presentation from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
- the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one pressing, in particular by means of predetermined predetermined breaking points making it easier to separate portioned smaller units.
- the portioned compacts can be designed as tablets, in cylinder or cuboid form, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
- Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts.
- the spatial shape of another embodiment of the shaped bodies is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the shaped bodies can be dosed directly into the induction chamber without metering aid, where they dissolve during the induction process.
- the shaped detergent tablets without problems in the washing drum via a metering aid or without a metering aid and is preferred in the context of the present invention.
- Another preferred shaped body that can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, are broken off and into the Machine can be entered.
- This principle of the "bar-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
- the various components are not pressed into a uniform tablet, but rather that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible for these different layers to have different dissolution rates. This can result in advantageous performance properties of the molded articles. If For example, components are contained in the moldings that mutually influence each other negatively, so it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted when the second goes into solution.
- the layer structure of the shaped bodies can be stacked, the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, but the inner layer (s) can also be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
- a shaped body consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while in the case of the stacked shaped body the two cover layers and in the case of the shaped body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in one molded body.
- Such multilayered moldings have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the wash liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without fear of stains from bleaching agents and the like.
- the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the method of melt coating.
- the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
- ⁇ ⁇ Dt
- ⁇ diametral fracture stress (DFS) in Pa
- P the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
- D is the molded body diameter in meters
- t the height of the moldings.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Detergent Compositions (AREA)
- Jellies, Jams, And Syrups (AREA)
- Seasonings (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Glanulating (AREA)
- Cosmetics (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2004/006464 WO2005123893A1 (de) | 2004-06-16 | 2004-06-16 | Gezielte granulation durch neutralisation im compomix |
DE502004010375T DE502004010375D1 (de) | 2004-06-16 | 2004-06-16 | Gezielte granulation durch neutralisation im compomix |
US11/629,598 US20080261857A1 (en) | 2004-06-16 | 2004-06-16 | Targeted Granulation Achieved by Neutralisation in a Compomix-Type Machine |
JP2007515786A JP2008502746A (ja) | 2004-06-16 | 2004-06-16 | コンポミックスマシーンにおいて中性化することにより得られるターゲット造粒 |
EP04739932A EP1756256B1 (de) | 2004-06-16 | 2004-06-16 | Gezielte granulation durch neutralisation im compomix |
AT04739932T ATE448289T1 (de) | 2004-06-16 | 2004-06-16 | Gezielte granulation durch neutralisation im compomix |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2004/006464 WO2005123893A1 (de) | 2004-06-16 | 2004-06-16 | Gezielte granulation durch neutralisation im compomix |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005123893A1 true WO2005123893A1 (de) | 2005-12-29 |
Family
ID=34958176
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/006464 WO2005123893A1 (de) | 2004-06-16 | 2004-06-16 | Gezielte granulation durch neutralisation im compomix |
Country Status (6)
Country | Link |
---|---|
US (1) | US20080261857A1 (de) |
EP (1) | EP1756256B1 (de) |
JP (1) | JP2008502746A (de) |
AT (1) | ATE448289T1 (de) |
DE (1) | DE502004010375D1 (de) |
WO (1) | WO2005123893A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005038070A1 (de) * | 2005-08-10 | 2007-03-15 | Henkel Kgaa | Wasch- und Reinigungsmittel mit gut löslichen Kapseln |
DE102012217877A1 (de) * | 2012-10-01 | 2013-08-14 | Henkel Ag & Co. Kgaa | Nontower-Verfahren |
CA3086996A1 (en) * | 2017-12-27 | 2019-07-04 | Toray Industries, Inc. | Method for collecting nucleic acid |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992006170A1 (en) * | 1990-10-03 | 1992-04-16 | The Procter & Gamble Company | Process for preparing high density detergent compositions containing particulate ph sensitive surfactant |
US5576285A (en) * | 1995-10-04 | 1996-11-19 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with an inorganic double salt |
JPH09241698A (ja) * | 1996-03-13 | 1997-09-16 | Lion Corp | 高嵩密度粒状洗剤組成物の製造方法 |
DE19858859A1 (de) * | 1998-12-19 | 2000-06-21 | Henkel Kgaa | Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate |
WO2004053046A1 (de) * | 2002-12-12 | 2004-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Trockenneutralisationsverfahren |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4587029A (en) * | 1983-06-27 | 1986-05-06 | The Chemithon Corporation | Intermediate product for use in producing a detergent bar |
DE4216774A1 (de) * | 1992-05-21 | 1993-11-25 | Henkel Kgaa | Verfahren zur kontinuierlichen Herstellung eines granularen Wasch und/oder Reinigungsmittels |
EP0862611B1 (de) * | 1995-11-06 | 2001-09-12 | Kao Corporation | Verfahren zur herstellung von kristallinen alkalimetallsilikaten und granulares waschmittel mit hoher schüttdichte |
GB9526097D0 (en) * | 1995-12-20 | 1996-02-21 | Unilever Plc | Process |
GB9712583D0 (en) * | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
GB0119708D0 (en) * | 2001-08-13 | 2001-10-03 | Unilever Plc | Process for the production of detergent granules |
-
2004
- 2004-06-16 US US11/629,598 patent/US20080261857A1/en not_active Abandoned
- 2004-06-16 AT AT04739932T patent/ATE448289T1/de not_active IP Right Cessation
- 2004-06-16 EP EP04739932A patent/EP1756256B1/de not_active Revoked
- 2004-06-16 WO PCT/EP2004/006464 patent/WO2005123893A1/de active Application Filing
- 2004-06-16 DE DE502004010375T patent/DE502004010375D1/de not_active Expired - Fee Related
- 2004-06-16 JP JP2007515786A patent/JP2008502746A/ja not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992006170A1 (en) * | 1990-10-03 | 1992-04-16 | The Procter & Gamble Company | Process for preparing high density detergent compositions containing particulate ph sensitive surfactant |
US5576285A (en) * | 1995-10-04 | 1996-11-19 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with an inorganic double salt |
JPH09241698A (ja) * | 1996-03-13 | 1997-09-16 | Lion Corp | 高嵩密度粒状洗剤組成物の製造方法 |
DE19858859A1 (de) * | 1998-12-19 | 2000-06-21 | Henkel Kgaa | Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate |
WO2004053046A1 (de) * | 2002-12-12 | 2004-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Trockenneutralisationsverfahren |
Non-Patent Citations (2)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 01 30 January 1998 (1998-01-30) * |
PIETSCH W: "SYSTEMATISCHE ENTWICKLUNG VON VERFAHREN ZUR KORNVERGROESSERUNG DURCH AGGLOMERIEREN SYSTEMATIC DEVELOPMENT OF PROCESSES FOR THE SIZE ENLARGEMENT BY AGGLOMERATION", November 2002, CHEMIE. INGENIEUR. TECHNIK, VERLAG CHEMIE GMBH. WEINHEIM, DE, PAGE(S) 1517-1519,1521, ISSN: 0009-286X, XP001132622 * |
Also Published As
Publication number | Publication date |
---|---|
ATE448289T1 (de) | 2009-11-15 |
US20080261857A1 (en) | 2008-10-23 |
EP1756256A1 (de) | 2007-02-28 |
DE502004010375D1 (de) | 2009-12-24 |
EP1756256B1 (de) | 2009-11-11 |
JP2008502746A (ja) | 2008-01-31 |
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