EP3839026B1 - Method for increasing the stability of cleaning agents - Google Patents
Method for increasing the stability of cleaning agents Download PDFInfo
- Publication number
- EP3839026B1 EP3839026B1 EP20209176.5A EP20209176A EP3839026B1 EP 3839026 B1 EP3839026 B1 EP 3839026B1 EP 20209176 A EP20209176 A EP 20209176A EP 3839026 B1 EP3839026 B1 EP 3839026B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- surfactant
- component
- added
- thickener
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 claims 1
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- 235000011082 potassium citrates Nutrition 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to a specific process for producing cleaning agents, in particular gel-form cleaning agents, and to a cleaning agent obtained by the process, in particular a dishwashing agent.
- cleaning agents are known from EN 10 2013 226301 A1 , WO 2012/044929 A2 and EN 10 2012 222266 A1 .
- gel-type cleaning agents in particular dishwashing detergents
- one challenge is to provide a long storage stability for the corresponding gels.
- gel-type cleaning agents with multiple cleaning components can tend to form phase separation after a certain time, which can be visually recognized by the formation of a layer, and can tend to reduce chemical stability, which can be visually recognized by the formation of flakes, usually white.
- the object of the present invention was therefore to provide a gel-type cleaning agent which in particular contains at least one thickener, at least one surfactant, at least one sulfopolymer and at least one complexing agent, which has a long storage stability and is obtainable by a relatively simple production process.
- the inventors of the present invention have surprisingly found that this problem can be solved by using a special process in which the cleaning agent components are added in a specific order.
- the thickener must be added before the at least one surfactant, the at least one sulfopolymer and the at least one complexing agent and the stirring speed in the container must be increased at least once.
- the invention relates to a cleaning agent obtained by the process according to the present invention.
- At least one refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compounds described herein, this statement does not refer to the absolute amount of molecules, but to the type of component. "At least one thickener” therefore means, for example, that only one type of thickener or several different types of thickeners can be included, without specifying the amount of the individual compounds.
- Gel or gel-like compositions or agents within the meaning of the present invention are those which have a viscosity of 50 to 500 mPas, preferably 100 to 300 mPas.
- the viscosity can be determined with a Brookfield LVDV II+ laboratory viscometer at 20°C using spindle 31 and 30 rpm.
- the expression "essentially free of” means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components.
- the property "essentially free of” a particular compound is therefore preferably considered to mean a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of the composition.
- Numerical ranges specified in the format "in/from x to y" include the specified values. If multiple preferred numerical ranges are specified in this format, it is It goes without saying that all areas resulting from the combination of the different endpoints are also recorded.
- molecular weight refers to the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly stated.
- Molecular weights are preferably determined by GPC using polystyrene standards.
- all components are added sequentially.
- the stirring speed is increased by 5 to 75% from the previous stirring speed up to the maximum speed, more preferably after every component, the stirring speed is increased by 5 to 40% from the previous stirring speed. In a preferred embodiment, the stirring speed is increased twice.
- the at least one thickener is added before the at least one surfactant (2), the at least one sulfopolymer (3) and the at least one complexing agent (4), and between the addition of the at least one thickener (1) and one or more of the components (2)-(4), at least one further component different from these components and/or water is added.
- Suitable surfactants are cationic, anionic, nonionic or zwitterionic surfactants or mixtures thereof.
- Anionic and/or nonionic surfactants are preferred.
- Such surfactants are known in the prior art.
- fatty alcohol alkoxylates more preferably fatty alcohol ethoxylates or propoxylates or their mixed ethers, in particular with a carbon chain length of the fatty alcohol of C 11-18 , particularly preferably C 11 and C 16-18 .
- the fatty alcohol alkoxylates preferably have 2 to 100, more preferably 5 to 50 alkoxylate units, in particular ethoxylate and/or propoxylate.
- a commercially available fatty alcohol alkoxylate is, for example, Dehypon E127 from BASF AG.
- the at least one thickener is selected from the group of polyacrylate (co)polymers. All polyacrylate (co)polymers known to the person skilled in the art which have a thickening effect for producing gels are suitable. For example, such polymers are available under the trade name Acusol from Dow Corning Inc., Acusol 810 and 820 are particularly suitable.
- the at least one thickener preferably has an M n of 1,000 to 1,000,000 g/mol, more preferably 5,000 to 100,000 g/mol, preferably measured by GPC using polystyrene standards.
- the at least one thickener preferably has a viscosity of 100 to 500 mPas, more preferably 100 to 300 mPas, preferably measured with a Brookfield viscometer with spindle 2, at 12 rpm and 25°C. In one embodiment, the at least one thickener preferably has a density of 1.02 to 1.05 g/cm 3 , in particular of 1.049 g/cm 3 .
- All sulfopolymers known to the person skilled in the art which can be used in cleaning agents are suitable as the at least one sulfopolymer.
- a copolymeric polysulfonate preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer.
- the copolymers can have two, three, four or more different monomer units.
- preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.
- unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
- Unsaturated dicarboxylic acids can of course also be used.
- Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, Vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-
- the sulfonic acid groups can be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
- metal ions preferably alkali metal ions and in particular for sodium ions.
- partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
- the monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, the monomers are preferably selected from those mentioned above.
- the molecular weight of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
- Preferred copolymers have molecular weights of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
- such polymers are available under the trade name Acusol from Dow Corning Inc.
- Acusol 590 or Acusol 588 are particularly suitable.
- the complexing agents are selected from the group of aminocarboxylic acids and their salts, for example, methylglycinediacetic acid (MGDA) or its salts, glutaminediacetic acid (GLDA) or its salts, ethylenediaminediacetic acid or its salts (EDDS) or mixtures thereof.
- MGDA methylglycinediacetic acid
- GLDA glutaminediacetic acid
- EDDS ethylenediaminediacetic acid or its salts
- suitable complexing agents are, for example, in the DE 102015206485 A1 , EP3080236A1 or DE 102015213938 A1
- a suitable commercially available complexing agent is available, for example, under the trade name Trilon Ultimate 2L from BASF AG.
- the at least one complexing agent is selected from citric acid and the salts of citric acid.
- the at least one complexing agent is trisodium citrate. In cases where citric acid or one of its salts is used as a complexing agent, this can simultaneously act as a pH adjuster and/or buffer substance. A further addition of a separate pH adjuster or buffer substance may then be dispensable. In such cases, the specified quantity limits for the complexing agent then apply to the total amount of the specified compound in the composition, regardless of the function.
- the at least one surfactant (2) comprises a surfactant from the group of hydroxy mixed ethers, in particular fatty alcohol alkoxylates.
- the at least one sulfopolymer (3) is a polymer from the group of acrylate copolymers, preferably containing acrylamidopropanesulfonic acid units.
- the at least one complexing agent (4) is selected from organic complexing agents, preferably from aminocarboxylic acids and their salts, more preferably from MGDA and GLDA and their salts, or from citric acid and their salts, more preferably trisodium citrate.
- the order of addition of components (1)-(4) is such that component (1) is added first, then component (3), then component (4) and then component (2), wherein between the addition of the at least one thickener (1) and component (3) preferably at least one further component different from these components and/or water is added, particularly preferably at least one structuring agent, in particular sorbitol.
- the order of addition of components (1)-(4) is such that component (1) is added first, then component (3), then component (4) and then component (2), wherein between the addition of the at least one thickener (1) and component (3) sorbitol is added and between the addition of component (4) and component (2) water is added, preferably in up to 5% by weight based on the total weight of the composition, and after the addition of component (2) at least one pH adjuster, in particular citric acid, and then at least one enzyme are added.
- the initial stirring speed is 30 rpm, preferably 35 rpm and/or the stirring speed upon addition of the last component is 80 rpm, preferably 70 rpm.
- the stirring speed is increased from 30 or 35 rpm to 80 or 70 rpm in one step, in a more preferred embodiment, it is increased in two steps.
- the stirring speed is increased from 35 rpm to 40 rpm after the addition of at least one sulfopolymer (3) and increased to 70 rpm after the addition of the at least one complexing agent (4).
- the stirring speed is 4000-11000dR ⁇ 2/3 depending on the stirrer diameter.
- the stirring speed can be increased in steps of 500-3000*dR ⁇ 2/3, preferably 1500-3000*dR ⁇ 2/3, particularly preferably 2500-3000*dR ⁇ 2/3. Where dR is the stirrer diameter.
- a dynamic mixer is additionally used for stirring.
- the container fill level before dosing the thickener (1) is about 30%, before dosing the sulfopolymer (3) about 47%, before dosing the complexing agent (4) about 63% and before dosing the surfactant (2) about 88%, based on the volume of the container.
- the stirrer is located in the container below the liquid surface.
- Preferred stirred tanks have volumes of 10 to 500,000 L.
- the ratio of height to diameter is preferably 1 to 2.2, more preferably 1.3 to 1.7.
- Common bottoms are dished, basket-arch and other curved bottoms, as well as conical bottoms.
- Examples of stirrer types are propeller, interprop, inclined blade or intermig stirrers.
- the respective mixture is stirred for at least 15 minutes after the dosing of the thickener (1), for at least 10 minutes after the dosing of the sulfopolymer (3), for at least 5 minutes after the dosing of the complexing agent (4) and for at least 5 minutes after the dosing of the surfactant (2).
- the at least one thickener preferably at least one acrylate (co)polymer
- the at least one surfactant is used in 0.1 to 10 wt.%, preferably 1 to 7 wt.%, more preferably 2.5 to 5 wt.%.
- the at least one sulfopolymer is used in 0.1 to 20 wt.%, preferably 5 to 17.5 wt.%, more preferably 10 to 15 wt.%.
- the at least one complexing agent is used in 1 to 35 wt.%, preferably 5 to 35 wt.%, more preferably 15 to 30 wt.%.
- water is used in 5 to 70 wt.%, preferably 10 to 55 wt.%, more preferably 20 to 45 wt.%. The weight percentages are based on the total weight of the cleaning agent.
- At least one further component selected from inorganic salts, dyes, pigments, preservatives, pH adjusters, structuring agents, such as sorbitol, trehalose, urea, glycerin, 1,2-propaniol, 1,3-propanediol, xylose, xylitol, in particular sorbitol, perfumes and enzymes is also included.
- the pH of the composition can be adjusted by means of conventional pH adjusters, for example acids such as mineral acids or organic acids, such as citric acid, and/or alkalis such as sodium or potassium hydroxide, whereby - particularly if hand compatibility is desired - a range of 6 to 10, preferably 6.5 to 9, most preferably 7.0 to 8.5, is desired.
- acids such as mineral acids or organic acids, such as citric acid
- alkalis such as sodium or potassium hydroxide
- one or more buffer substances can be added to the composition in the process according to the invention as pH adjusters. are added, usually in amounts of 0.001 to 5 wt.%, preferably 0.005 to 3 wt.%, more preferably 0.01 to 2 wt.%, even more preferably 0.05 to 1 wt.%, most preferably 0.1 to 0.5 wt.%, for example 0.2 wt.%.
- Preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate ⁇ 2 H 2 O and tripotassium citrate ⁇ H 2 O. As already described above, the citrates also function as complexing agents. If citrates are used as complexing agents, the use of other buffer substances may be obsolete.
- the at least one further component is at least one enzyme, more preferably a protease.
- the proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, i.e. they hydrolyze any acid amide bonds that are located inside peptides or proteins and thereby cause the degradation of protein-containing soiling on the items being cleaned.
- subtilisin 309 examples of the proteases that can be used in the process according to the invention are subtilisin 309 or functional fragments/variants thereof and variants of the alkaline protease from Bacillus lentus or variants thereof.
- Subtilisin 309 is sold under the trade name Savinase ® by Novozymes A/S, Bagsvaerd, Denmark.
- Optimized enzyme variants of subtilisin 309 from Bacillus lentus are available under the trade names Blaze ® and Ovozyme ® from Novozymes, which represent a preferred embodiment of the invention.
- the protease variants known under the name BLAP ® are derived from the alkaline protease from Bacillus lentus DSM 5483, for example.
- Preferred protease variants are those that, compared to the BLAP wt (wild type) enzyme, in the count according to BLAP wt, have at least one mutation at R99 in particular R99E or R99D, particularly preferred is R99E, and optionally additionally at least one or two, preferably all three of the amino acid substitutions S3T, V4I and V199I, particularly preferred are the BLAP variants as described in SeqlD No 4 or 5 of the WO2014/177430 are described.
- the enzymes that can be used as an optional component can also be packaged together with accompanying substances, for example from fermentation.
- the enzymes are preferably used as enzyme liquid formulation(s).
- the proteases are generally not provided in the form of pure protein, but rather in the form of stabilized, storable and transportable preparations.
- These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, preferably, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other additives.
- the enzymes can be encapsulated, 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 enzymes are enclosed as if in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer that is impermeable to water, air and/or chemicals.
- active ingredients such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, can be applied in superimposed layers.
- Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes.
- Such granules, for example by applying polymeric film formers are advantageously low in dust and are stable in storage due to the coating.
- enzymes especially amylases, hemicellulases, cellulases, lipases and oxidoreductases, can also be added.
- the amylase(s) is/are preferably an ⁇ -amylase.
- the hemicellulase is preferably a ⁇ -glucanase, a pectinase, a pullulanase and/or a mannanase.
- the cellulase is preferably a cellulase mixture or a single-component cellulase, preferably or predominantly an endoglucanase and/or a cellobiohydrolase.
- the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
- the enzymes mentioned can all be formulated as described above for the proteases.
- the at least one further component comprises a protease in an amount of 0.01 to 1.6 wt.%, preferably 0.08 to 1.2 wt.%, based on the total weight of the composition.
- the enzyme(s) can be preformulated with enzyme stabilizers in an enzyme composition.
- the enzyme protein usually only forms a fraction of the total weight of the enzyme preparation.
- Preferably used enzyme preparations contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and most preferably between 0.8 and 10% by weight of the enzyme protein.
- an enzyme stabilizer can be contained in an amount of 0.05 to 35% by weight, preferably from 0.05 to 10% by weight, based on the total weight in the enzyme composition.
- This enzyme composition can then be added as an additive in the process according to the invention in amounts that lead to the final concentrations in the composition specified above.
- Suitable enzyme stabilizers are known in the prior art.
- one or more enzyme stabilizers can accordingly also be added in the process according to the invention.
- the protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
- the determination of the active protein concentration is carried out by titrating the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).
- a suitable irreversible inhibitor for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)
- less than 5% by weight of organic solvents are included, based on the total weight of the cleaning agent. In a preferred embodiment, essentially no organic solvents are included. In one embodiment, less than 6% by weight of thickeners that are not acrylate (co)polymers are included, based on the total weight of the cleaning agent. In a preferred embodiment, only acrylate (co)polymers are included as thickeners.
- the invention relates to a cleaning agent obtained by the process according to the present invention, wherein the cleaning agent is preferably a dishwashing agent.
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
Die vorliegende Erfindung betrifft ein spezifisches Verfahren zur Herstellung von Reinigungsmitteln, insbesondere gelförmigen Reinigungsmitteln und ein durch das Verfahren erhaltene Reinigungsmittel, insbesondere ein Geschirrspülmittel. Solche Reinigungsmittel sind bekannt aus
Auf dem Gebiet der gelförmigen Reinigungsmittel, insbesondere der Geschirrspülmittel, ist eine Herausforderung die Bereitstellung einer langen Lagerstabilität der entsprechenden Gele. Insbesondere können gelförmige Reinigungsmittel mit mehreren Reinigungskomponenten nach einer gewissen Zeit zur Bildung von Phasentrennung neigen, was optisch durch eine Schichtbildung zu erkennen ist, und Verringerung der chemischen Stabilität neigen, was optisch durch eine, meist weiße, Flockenbildung zu bemerken ist. Diese optischen und chemischen Veränderungen sind vom Verbraucher unerwünscht. Aufgabe der vorliegenden Erfindung war es deshalb ein gelförmiges Reinigungsmittel, welches insbesondere mindestens einen Verdicker, mindestens ein Tensid, mindestens ein Sulfopolymer und mindestens einen Komplexbildner enthält, bereitzustellen, welches eine lange Lagerstabilität aufweist und durch ein relativ einfaches Herstellungsverfahren erhältlich ist.In the field of gel-type cleaning agents, in particular dishwashing detergents, one challenge is to provide a long storage stability for the corresponding gels. In particular, gel-type cleaning agents with multiple cleaning components can tend to form phase separation after a certain time, which can be visually recognized by the formation of a layer, and can tend to reduce chemical stability, which can be visually recognized by the formation of flakes, usually white. These optical and chemical changes are undesirable for consumers. The object of the present invention was therefore to provide a gel-type cleaning agent which in particular contains at least one thickener, at least one surfactant, at least one sulfopolymer and at least one complexing agent, which has a long storage stability and is obtainable by a relatively simple production process.
Die Erfinder der vorliegenden Erfindung haben hierbei überraschend gefunden, dass dieses Problem durch die Verwendung eines speziellen Verfahrens gelöst werden kann, in dem eine spezielle Reihenfolge der Zugabe der Reinigungsmittelkomponenten erfolgt. Dabei muss der Verdicker vor dem mindestens einen Tensid, dem mindestens einen Sulfopolymer und dem mindestens einen Komplexbildner zugegeben werden und die Rührgeschwindigkeit im Behälter mindestens einmal erhöht werden.The inventors of the present invention have surprisingly found that this problem can be solved by using a special process in which the cleaning agent components are added in a specific order. The thickener must be added before the at least one surfactant, the at least one sulfopolymer and the at least one complexing agent and the stirring speed in the container must be increased at least once.
Deshalb betrifft die Erfindung in einem ersten Aspekt ein Verfahren zur Herstellung von Reinigungsmitteln, umfassend die Schritte:
- (i) Vorlegen von Wasser in einem Behälter, welcher eine Rührvorrichtung enthält;
- (ii) Zugeben der Reinigungsmittelkomponenten in das Wasser unter Rühren, um ein Reinigungsmittel zu erhalten; wobei
- (1) mindestens ein Verdicker ausgewählt aus der Gruppe der Polyacrylat-(Co)Polymere,
- (2) mindestens ein Tensid,
- (3) mindestens ein Sulfopolymer und
- (4) mindestens ein Komplexbildner zugegeben werden, mit der Maßgabe, dass die Komponenten (1)-(4) jeweils separat zugegeben werden;
- dass der mindestens eine Verdicker (1) vor dem mindestens einen Tensid (2), dem mindestens einen Sulfopolymer (3) und dem mindestens einen Komplexbildner (4) zugegeben wird; und
- die Rührgeschwindigkeit bei jeder Zugabe gleich bleibt oder erhöht wird, jedoch mindestens einmal nach der ersten Zugabe erhöht wird.
- (i) placing water in a container containing a stirring device;
- (ii) adding the detergent components to the water with stirring to obtain a detergent; wherein
- (1) at least one thickener selected from the group of polyacrylate (co)polymers,
- (2) at least one surfactant,
- (3) at least one sulfopolymer and
- (4) at least one complexing agent is added, with the proviso that components (1)-(4) are each added separately;
- that the at least one thickener (1) is added before the at least one surfactant (2), the at least one sulphopolymer (3) and the at least one complexing agent (4); and
- the stirring speed remains the same or is increased with each addition, but is increased at least once after the first addition.
In einem zweiten Aspekt betrifft die Erfindung ein Reinigungsmittel, erhalten durch das Verfahren gemäß der vorliegenden Erfindung.In a second aspect, the invention relates to a cleaning agent obtained by the process according to the present invention.
"Mindestens ein", wie hierin verwendet, bezieht sich auf 1 oder mehr, beispielsweise 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Im Zusammenhang mit Bestandteilen der hierin beschriebenen Verbindungen bezieht sich diese Angabe nicht auf die absolute Menge an Molekülen, sondern auf die Art des Bestandteils. "Mindestens ein Verdicker" bedeutet daher beispielsweise, dass nur eine Art von Verdicker oder mehrere verschiedene Arten von Verdickern, ohne Angaben über die Menge der einzelnen Verbindungen zu machen, enthalten sein können."At least one" as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compounds described herein, this statement does not refer to the absolute amount of molecules, but to the type of component. "At least one thickener" therefore means, for example, that only one type of thickener or several different types of thickeners can be included, without specifying the amount of the individual compounds.
Gel oder gelförmige Zusammensetzungen oder Mittel im Sinne der vorliegenden Erfindung sind solche, welche eine Viskosität von 50 bis 500 mPas, bevorzugt 100 bis 300 mPas, aufweisen. Die Viskosität kann dabei mit einem Brookfield LVDV II+ Laborviskosimeter bei 20°C unter Verwendung von Spindel 31 und 30 Upm bestimmt werden.Gel or gel-like compositions or agents within the meaning of the present invention are those which have a viscosity of 50 to 500 mPas, preferably 100 to 300 mPas. The viscosity can be determined with a Brookfield LVDV II+ laboratory viscometer at 20°C using spindle 31 and 30 rpm.
Alle im Zusammenhang mit den hierin beschriebenen Zusammensetzungen angegeben Mengenangaben beziehen sich, sofern nichts anderes angegeben ist, auf Gew.-% jeweils bezogen auf das Gesamtgewicht der Zusammensetzung. Des Weiteren beziehen sich derartige Mengenangaben, die sich auf mindestens einen Bestandteil beziehen, immer auf die Gesamtmenge dieser Art von Bestandteil, die in der Zusammensetzung enthalten ist, sofern nicht explizit etwas anderes angegeben ist. Das heißt, dass sich derartige Mengenangaben, beispielsweise im Zusammenhang mit "mindestens einem Verdicker", auf die Gesamtmenge von Verdickern, welche in der Zusammensetzung enthalten sind, bezieht, wenn nicht explizit etwas anderes angegeben ist.All quantities given in connection with the compositions described herein refer, unless otherwise stated, to % by weight, in each case based on the total weight of the composition. Furthermore, such quantities which refer to at least one component always refer to the total amount of this type of component contained in the composition, unless explicitly stated otherwise. This means that such quantities, for example in connection with "at least one thickener", refer to the total amount of thickeners contained in the composition, unless explicitly stated otherwise.
Zahlenwerte, die hierin ohne Dezimalstellen angegeben sind, beziehen sich jeweils auf den vollen angegebenen Wert mit einer Dezimalstelle. So steht beispielsweise "99 %" für "99,0 %".Numerical values given without decimal places refer to the full value given with one decimal place. For example, "99%" stands for "99.0%".
Der Ausdrücke "ungefähr" "ca." oder "etwa", in Zusammenhang mit einem Zahlenwert, bezieht sich auf eine Varianz von ±10 % bezogen auf den angegebenen Zahlenwert, bevorzugt ±5 %, besonders bevorzugt ±1 %, noch stärker bevorzugt unter ± 0,1 %.The terms "approximately", "ca." or "about", in connection with a numerical value, refers to a variance of ±10% based on the stated numerical value, preferably ±5%, particularly preferably ±1%, even more preferably below ±0.1%.
Der Ausdruck "im Wesentlichen frei von" bedeutet, dass die jeweilige Verbindung grundsätzlich enthalten sein kann, dann allerdings in einer Menge vorliegt, die eine Funktion der anderen Komponenten nicht beeinträchtigt. Im Rahmen der vorliegenden Erfindung wird daher unter der Eigenschaft "im Wesentlichen frei von" einer bestimmten Verbindung bevorzugt ein Gesamtgewicht von unter 0,1 Gew.-%, stärker bevorzugt unter 0,001 Gew.-%, insbesondere frei von dieser, bezogen auf das Gesamtgewicht der Zusammensetzung, angesehen.The expression "essentially free of" means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components. In the context of the present invention, the property "essentially free of" a particular compound is therefore preferably considered to mean a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of the composition.
Numerische Bereiche, die in dem Format "in/von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden.Numerical ranges specified in the format "in/from x to y" include the specified values. If multiple preferred numerical ranges are specified in this format, it is It goes without saying that all areas resulting from the combination of the different endpoints are also recorded.
Angaben über das Molekulargewicht beziehen sich auf das gewichtsmittlere Molekulargewicht in g/mol, falls nicht explizit das zahlenmittlere Molekulargewicht genannt ist. Molekulargewichte werden bevorzugt mittels GPC unter Verwendung von Polystyrol-Standards ermittelt.Information on molecular weight refers to the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly stated. Molecular weights are preferably determined by GPC using polystyrene standards.
Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal oder jede Ausführungsform aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Beispielweise können beschriebene Merkmale oder Ausführungsformen des Verfahrens auch auf das beanspruchte Reinigungsmittel angewendet werden, und umgekehrt. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist.These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature or embodiment from one aspect of the invention can be used in any other aspect of the invention. For example, described features or embodiments of the method can also be applied to the claimed cleaning agent, and vice versa. Furthermore, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples.
Die Erfindung betrifft ein Verfahren zur Herstellung von Reinigungsmitteln, insbesondere gelförmigen Reinigungsmittel, umfassend oder bestehend aus den Schritten:
- (i) Vorlegen von Wasser in einem Behälter, welcher eine Rührvorrichtung enthält, insbesondere einem Rührkessel;
- (ii) Zugeben der Reinigungsmittelkomponenten in das Wasser, bevorzugt mittels mindestens einer Dosierpumpe, insbesondere mittels einer Dosierpumpe, unter Rühren, um ein Reinigungsmittel zu erhalten; wobei
- (1) mindestens ein Verdicker ausgewählt aus der Gruppe der Polyacrylat-(Co)Polymere,
- (2) mindestens ein Tensid,
- (3) mindestens ein Sulfopolymer und
- (4) mindestens ein Komplexbildner zugegeben werden, mit der Maßgabe, dass die Komponenten (1)-(4) jeweils separat zugegeben werden;
- dass der mindestens eine Verdicker (1) vor dem mindestens einen Tensid (2), dem mindestens einen Sulfopolymer (3) und dem mindestens einen Komplexbildner (4) zugegeben wird; und
- die Rührgeschwindigkeit bei jeder Zugabe gleich bleibt oder erhöht wird, jedoch mindestens einmal nach der ersten Zugabe erhöht wird.
- (i) placing water in a container containing a stirring device, in particular a stirred tank;
- (ii) adding the cleaning agent components to the water, preferably by means of at least one metering pump, in particular by means of a metering pump, with stirring to obtain a cleaning agent; wherein
- (1) at least one thickener selected from the group of polyacrylate (co)polymers,
- (2) at least one surfactant,
- (3) at least one sulfopolymer and
- (4) at least one complexing agent is added, with the proviso that components (1)-(4) are each added separately;
- that the at least one thickener (1) is added before the at least one surfactant (2), the at least one sulphopolymer (3) and the at least one complexing agent (4); and
- the stirring speed remains the same or is increased with each addition, but is increased at least once after the first addition.
In einer Ausführungsform werden alle Komponenten sequenziell zugegeben. In einer weiteren Ausführungsform wird nach jeder zweiten Komponente die Rührgeschwindigkeit bis zur maximalen Geschwindigkeit um jeweils 5 bis 75 % ausgehend von der vorherigen Rührgeschwindigkeit erhöht, stärker bevorzugt wird nach jeder Komponente die Rührgeschwindigkeit um 5 bis 40% ausgehend von der vorherigen Rührgeschwindigkeit erhöht. In einer bevorzugten Ausführungsform wird die Rührgeschwindigkeit zweimal erhöht.In one embodiment, all components are added sequentially. In another embodiment, after every second component, the stirring speed is increased by 5 to 75% from the previous stirring speed up to the maximum speed, more preferably after every component, the stirring speed is increased by 5 to 40% from the previous stirring speed. In a preferred embodiment, the stirring speed is increased twice.
In einer Ausführungsform wird der mindestens eine Verdicker vor dem mindestens einen Tensid (2), dem mindestens einen Sulfopolymer (3) und dem mindestens einen Komplexbildner (4) zugegeben und zwischen der Zugabe des mindestens einen Verdickers (1) und einem oder mehreren der Komponenten (2)-(4) wird mindestens eine weitere, von diesen Komponenten verschiedene Komponente und/oder Wasser zugegeben.In one embodiment, the at least one thickener is added before the at least one surfactant (2), the at least one sulfopolymer (3) and the at least one complexing agent (4), and between the addition of the at least one thickener (1) and one or more of the components (2)-(4), at least one further component different from these components and/or water is added.
Geeignete Tenside sind kationische, anionische, nichtionische oder zwitterionische Tenside oder Mischungen davon. Bevorzugt sind anionische und/oder nichtionische Tenside. Beispielsweise Tenside ausgewählt aus Alkylbenzolsulfonaten, Alkylsulfaten, Alkylestersulfonaten, sekundären Alkansulfonaten, Fettalkoholalkoxylaten, Alkylglykosiden, alkoxylierten Fettsäurealkylestern, Fettsäurealkanolamiden, Hydroxymischethern, Sorbitanfettsäurestern, Polyhydroxyfettsäureamiden und alkoxylierten Alkoholen. Derartige Tenside sind im Stand der Technik bekannt. Besonders bevorzugt sind Fettalkoholalkoxylate, stärker bevorzugt Fettalkoholethoxylate oder - propoxylate oder deren Mischether, insbesondere mit einer Kohlenstoffkettenlänge des Fettalkohols von C11-18, besonders bevorzugt C11 und C16-18. Bevorzugt weisen die Fettalkoholalkoxylate 2 bis 100, stärker bevorzugt 5 bis 50 Alkoxylateinheiten auf, insbesondere Ethoxylat und/oder Propoxylat. Ein kommerziell erhältliches Fettalkoholalkoxylat ist beispielsweise Dehypon E127 der Firma BASF AG.Suitable surfactants are cationic, anionic, nonionic or zwitterionic surfactants or mixtures thereof. Anionic and/or nonionic surfactants are preferred. For example, surfactants selected from alkylbenzenesulfonates, alkyl sulfates, alkyl ester sulfonates, secondary alkanesulfonates, fatty alcohol alkoxylates, alkyl glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides and alkoxylated alcohols. Such surfactants are known in the prior art. Particular preference is given to fatty alcohol alkoxylates, more preferably fatty alcohol ethoxylates or propoxylates or their mixed ethers, in particular with a carbon chain length of the fatty alcohol of C 11-18 , particularly preferably C 11 and C 16-18 . The fatty alcohol alkoxylates preferably have 2 to 100, more preferably 5 to 50 alkoxylate units, in particular ethoxylate and/or propoxylate. A commercially available fatty alcohol alkoxylate is, for example, Dehypon E127 from BASF AG.
Der mindestens eine Verdicker ist aus der Gruppe der Polyacrylat-(Co)Polymere ausgewählt. Dabei sind alle dem Fachmann bekannten Polyacrylat-(Co)Polymere, welche eine verdickende Wirkung zur Erzielung von Gelen aufweisen geeignet. Beispielsweise sind solche Polymere unter dem Handelsnamen Acusol von der Firma Dow Corning Inc. erhältlich, insbesondere geeignet sind dabei Acusol 810 und 820. In einer Ausführungsform weist der mindestens eine Verdicker bevorzugt ein Mn von 1.000 bis 1.000.000 g/mol auf, stärker bevorzugt 5.000 bis 100.000 g/mol, bevorzugt gemessen mittels GPC unter der Verwendung von Polystyrolstandards. In einer Ausführungsform weist der mindestens eine Verdicker bevorzugt eine Viskosität von 100 bis 500 mPas, stärker bevorzugt 100 bis 300 mPas auf, bevorzugt gemessen mit einem Brookfield Viskosimeter mit Spindel 2, bei 12 upm und 25°C. In einer Ausführungsform weist der mindestens eine Verdicker bevorzugt eine Dichte von 1,02 bis 1,05 g/cm3 auf, insbesondere von 1,049 g/cm3.The at least one thickener is selected from the group of polyacrylate (co)polymers. All polyacrylate (co)polymers known to the person skilled in the art which have a thickening effect for producing gels are suitable. For example, such polymers are available under the trade name Acusol from Dow Corning Inc., Acusol 810 and 820 are particularly suitable. In one embodiment, the at least one thickener preferably has an M n of 1,000 to 1,000,000 g/mol, more preferably 5,000 to 100,000 g/mol, preferably measured by GPC using polystyrene standards. In one embodiment, the at least one thickener preferably has a viscosity of 100 to 500 mPas, more preferably 100 to 300 mPas, preferably measured with a Brookfield viscometer with spindle 2, at 12 rpm and 25°C. In one embodiment, the at least one thickener preferably has a density of 1.02 to 1.05 g/cm 3 , in particular of 1.049 g/cm 3 .
Als das mindestens eine Sulfopolymer sind alle dem Fachmann bekannten Sulfopolymere, welche in Reinigungsmittel eingesetzt werden können geeignet. Als Sulfopolymer wird vorzugsweise ein copolymeres Polysulfonat, vorzugsweise ein hydrophob modifiziertes copolymeres Polysulfonat, eingesetzt. Die Copolymere können zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen. Bevorzugte copolymere Polysulfonate enthalten neben Sulfonsäuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesättigten Carbonsäuren. Als ungesättigte Carbonsäure(n) wird/werden mit besonderem Vorzug ungesättigte Carbonsäuren der Formel R1(R2)C=C(R3)COOH eingesetzt, in der R1 bis R3 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für-COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.All sulfopolymers known to the person skilled in the art which can be used in cleaning agents are suitable as the at least one sulfopolymer. A copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer. The copolymers can have two, three, four or more different monomer units. In addition to monomer(s) containing sulfonic acid groups, preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids. The unsaturated carboxylic acid(s) used are particularly preferably unsaturated carboxylic acids of the formula R 1 (R 2 )C=C(R 3 )COOH, in which R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 Carbon atoms, alkyl or alkenyl radicals substituted with -NH 2 , -OH or -COOH as defined above or represents -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
Besonders bevorzugte ungesättigte Carbonsäuren sind Acrylsäure, Methacrylsäure, Ethacrylsäure, α-Chloroacrylsäure, α-Cyanoacrylsäure, Crotonsäure, α-Phenyl-Acrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäure, Methylenmalonsäure, Sorbinsäure, Zimtsäure oder deren Mischungen. Einsetzbar sind selbstverständlich auch die ungesättigten Dicarbonsäuren.Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Unsaturated dicarboxylic acids can of course also be used.
Bei den Sulfonsäuregruppen-haltigen Monomeren sind solche der Formel
R5(R6)C=C(R7)-X-SO3H
bevorzugt, in der R5 bis R7 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für-COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.The monomers containing sulfonic acid groups are those of the formula
R 5 (R 6 )C=C(R 7 )-X-SO 3 H
preferred, in which R 5 to R 7 independently of one another represent -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH 2 , -OH or -COOH or represent -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group which is selected from -(CH 2 ) n - with n = 0 to 4, -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 -, -C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.
Unter diesen Monomeren bevorzugt sind solche der Formeln
H2C=CH-X-SO3H
H2C=C(CH3)-X-SO3H
HO3S-X-(R6)C=C(R7)-X-SO3H,
in denen R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3, -CH2CH2CH3 und -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n-mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.Preferred among these monomers are those of the formulas
H 2 C=CH-X-SO 3 H
H 2 C=C(CH 3 )-X-SO 3 H
HO 3 SX-(R 6 )C=C(R 7 )-X-SO 3 H,
in which R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 and -CH(CH 3 ) 2 and X represents an optionally present spacer group selected from -(CH 2 ) n -with n = 0 to 4, -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 -, -C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.
Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acrylamido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methyl-1-propansulfonsäure, 2-Methacrylamido-2-methyl-1-propansulfonsäure, 3-Methacrylamido-2-hydroxy-propansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten Säuren oder deren wasserlösliche Salze.Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, Vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.
In den Polymeren können die Sulfonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. dass das acide Wasserstoffatom der Sulfonsäuregruppe in einigen oder allen Sulfonsäuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten sulfonsäuregruppenhaltigen Copolymeren ist erfindungsgemäß bevorzugt.In the polymers, the sulfonic acid groups can be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
Die Monomerenverteilung der erfindungsgemäß bevorzugt eingesetzten Copolymere beträgt bei Copolymeren, die nur Carbonsäuregruppen-haltige Monomere und Sulfonsäuregruppen-haltige Monomere enthalten, vorzugsweise jeweils 5 bis 95 Gew.-%, besonders bevorzugt beträgt der Anteil des Sulfonsäuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des Carbonsäuregruppen-haltigen Monomers 10 bis 50 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewählt aus den zuvor genannten.The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, the monomers are preferably selected from those mentioned above.
Die Molmasse der erfindungsgemäß bevorzugt eingesetzten Sulfo-Copolymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte Copolymere weisen Molmassen von 2000 bis 200.000 gmol-1, vorzugsweise von 4000 bis 25.000 gmol-1 und insbesondere von 5000 bis 15.000 gmol-1 auf.The molecular weight of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred copolymers have molecular weights of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
Beispielsweise sind solche Polymere unter dem Handelsnamen Acusol von der Firma Dow Corning Inc. erhältlich, insbesondere geeignet ist dabei Acusol 590 oder Acusol 588.For example, such polymers are available under the trade name Acusol from Dow Corning Inc. Acusol 590 or Acusol 588 are particularly suitable.
Als der mindestens eine Komplexbildner sind alle dem Fachmann bekannten Komplexbildner, welche in Reinigungsmittel eingesetzt werden können geeignet. In einer Ausführungsform sind die Komplexbildner aus der Gruppe der Aminocarbonsäuren und ihren Salzen ausgewählt, beispielsweise, Methylglycindiessigsäure (MGDA) oder ihre Salze, Glutamindiessigsäure (GLDA) oder ihre Salze, Ethylendiamindiessigsäure oder ihre Salze (EDDS) oder Mischungen davon. Weitere geeignete Komplexbildner sind beispielsweise in der
In einer weiteren Ausführungsform ist der mindestens eine Komplexbildner ausgewählt aus Zitronensäure und den Salzen der Zitronensäure. Vorzugsweise ist der mindestens eine Komplexbildner Trinatriumcitrat. In den Fällen, in denen Zitronensäure oder eines ihrer Salze als Komplexbildner eingesetzt wird, kann diese gleichzeitig als pH-Stellmittel und/oder Puffersubstanz wirken. Eine weitere Zugabe eines separaten pH-Stellmittels oder einer Puffersubstanz kann dann verzichtbar sein. Die angegebenen Mengengrenzen für den Komplexbildner gelten in solchen Fällen dann für die Gesamtmenge der angegebenen Verbindung in der Zusammensetzung unabhängig von der Funktion. In einer Ausführungsform umfasst das mindestens eine Tensid (2) ein Tensid aus der Gruppe der Hydroxymischether, insbesondere Fettalkoholalkoxylate. In einer Ausführungsform ist das mindestens eine Sulfopolymer (3) ein Polymer aus der Gruppe der Acrylat-Copolymere, vorzugsweise enthaltend Acrylamidopropansulfonsäure-Einheiten. In einer Ausführungsform wird der mindestens eine Komplexbildner (4) ausgewählt aus organischen Komplexbildnern, vorzugsweise aus Aminocarbonsäuren und deren Salzen, stärker bevorzugt aus MGDA und GLDA und deren Salzen, oder aus Zitronensäure und deren Salzen, stärker bevorzugt Trinatriumcitrat.In a further embodiment, the at least one complexing agent is selected from citric acid and the salts of citric acid. Preferably, the at least one complexing agent is trisodium citrate. In cases where citric acid or one of its salts is used as a complexing agent, this can simultaneously act as a pH adjuster and/or buffer substance. A further addition of a separate pH adjuster or buffer substance may then be dispensable. In such cases, the specified quantity limits for the complexing agent then apply to the total amount of the specified compound in the composition, regardless of the function. In one embodiment, the at least one surfactant (2) comprises a surfactant from the group of hydroxy mixed ethers, in particular fatty alcohol alkoxylates. In one embodiment, the at least one sulfopolymer (3) is a polymer from the group of acrylate copolymers, preferably containing acrylamidopropanesulfonic acid units. In one embodiment, the at least one complexing agent (4) is selected from organic complexing agents, preferably from aminocarboxylic acids and their salts, more preferably from MGDA and GLDA and their salts, or from citric acid and their salts, more preferably trisodium citrate.
In einer Ausführungsform erfolgt die Reihenfolge der Zugabe der Komponenten (1)-(4) derart, dass zuerst Komponente (1) zugegeben wird, dann Komponente (3), dann Komponente (4) und dann Komponente (2), wobei zwischen der Zugabe des mindestens einen Verdickers (1) und der Komponente (3) vorzugsweise mindestens eine weitere, von diesen Komponenten verschiedene Komponente und/oder Wasser zugegeben wird, besonders bevorzugt mindestens ein Strukturierungsmittel, insbesondere Sorbitol. In einer bevorzugten Ausführungsform erfolgt die Reihenfolge der Zugabe der Komponenten (1)-(4) derart, dass zuerst Komponente (1) zugegeben wird, dann Komponente (3), dann Komponente (4) und dann Komponente (2), wobei zwischen der Zugabe des mindestens einen Verdickers (1) und der Komponente (3) Sorbitol zugegeben wird und zwischen der Zugabe der Komponente (4) und der Komponente (2) Wasser zugegeben wird, bevorzugt in bis zu 5 Gew.-% basierend auf dem Gesamtgewicht der Zusammensetzung, und nach der Zugabe der Komponente (2) mindestens ein pH-Stellmittel, insbesondere Zitronensäure, und danach mindestens ein Enzym zugegeben werden.In one embodiment, the order of addition of components (1)-(4) is such that component (1) is added first, then component (3), then component (4) and then component (2), wherein between the addition of the at least one thickener (1) and component (3) preferably at least one further component different from these components and/or water is added, particularly preferably at least one structuring agent, in particular sorbitol. In a preferred embodiment, the order of addition of components (1)-(4) is such that component (1) is added first, then component (3), then component (4) and then component (2), wherein between the addition of the at least one thickener (1) and component (3) sorbitol is added and between the addition of component (4) and component (2) water is added, preferably in up to 5% by weight based on the total weight of the composition, and after the addition of component (2) at least one pH adjuster, in particular citric acid, and then at least one enzyme are added.
In einer Ausführungsform beträgt die anfängliche Rührgeschwindigkeit 30 Upm, bevorzugt 35 Upm und/oder die Rührgeschwindigkeit bei Zugabe der letzten Komponente 80 Upm, bevorzugt 70 Upm. In einer bevorzugten Ausführungsform wird die Rührgeschwindigkeit von 30 bzw. 35 Upm auf 80 bzw. 70 Upm in einem Schritt erhöht, in einer stärker bevorzugten Ausführungsform wird sie in zwei Schritten erhöht. In einer bevorzugten Ausführungsform wird die Rührgeschwindigkeit von 35 Upm auf 40 Upm nach der Zugabe von mindestens einem Sulfopolymer (3) erhöht und auf 70 Upm nach der Zugabe des mindesten einen Komplexbildners (4) erhöht.In one embodiment, the initial stirring speed is 30 rpm, preferably 35 rpm and/or the stirring speed upon addition of the last component is 80 rpm, preferably 70 rpm. In a preferred embodiment, the stirring speed is increased from 30 or 35 rpm to 80 or 70 rpm in one step, in a more preferred embodiment, it is increased in two steps. In a preferred embodiment, the stirring speed is increased from 35 rpm to 40 rpm after the addition of at least one sulfopolymer (3) and increased to 70 rpm after the addition of the at least one complexing agent (4).
In einer alternativen Ausführungsform beträgt die Rührgeschwindigkeit in Abhängigkeit des Rührerdurchmessers 4000-11000dR^2/3. Die Rührgeschwindigkeit kann dabei in Schritten von 500-3000*dR^2/3, bevorzugt 1500-3000*dR^2/3, besonders bevorzugt 2500-3000*dR^2/3, erhöht werden. Wobei dR der Rührerdurchmesser ist.In an alternative embodiment, the stirring speed is 4000-11000dR^2/3 depending on the stirrer diameter. The stirring speed can be increased in steps of 500-3000*dR^2/3, preferably 1500-3000*dR^2/3, particularly preferably 2500-3000*dR^2/3. Where dR is the stirrer diameter.
In einer Ausführungsform wird zusätzlich ein dynamischer Mischer zum Rühren verwendet.In one embodiment, a dynamic mixer is additionally used for stirring.
In einer Ausführungsform beträgt der Behälterfüllstand vor der Dosierung des Verdickers (1) etwa 30%, vor der Dosierung des Sulfopolymers (3) etwa 47%, vor der Dosierung des Komplexbildners (4) etwa 63% und vor der Dosierung des Tensids (2) etwa 88%, basierend auf dem Volumen des Behälters. Diese Füllstände sind vorteilhaft, da dadurch eine erhöhte Rührgeschwindigkeit ermöglicht werden kann.In one embodiment, the container fill level before dosing the thickener (1) is about 30%, before dosing the sulfopolymer (3) about 47%, before dosing the complexing agent (4) about 63% and before dosing the surfactant (2) about 88%, based on the volume of the container. These filling levels are advantageous because they allow for an increased stirring speed.
In einer Ausführungsform befindet sich der Rührer im Behälter unterhalb der Flüssigkeitsoberfläche.In one embodiment, the stirrer is located in the container below the liquid surface.
Bevorzugte Rührkessel weisen Volumina von 10 bis 500000 L auf. Das Verhältnis von Höhe zu Durchmesser beträgt bevorzugt 1 bis 2,2, stärker bevorzugt 1,3 bis 1,7. Übliche Böden sind Klöpper-, Korbbogen- und anderweitig gewölbte Böden, sowie konische Böden. Beispielhafte Rührertypen sind Propeller-, Interprop-, Schrägblatt- oder Intermig-Rührer. Dabei ist für die obigen Behälter eine Anzahl an Rührelementen von 1 bis 4, insbesondere 2 bis 3, bevorzugt.Preferred stirred tanks have volumes of 10 to 500,000 L. The ratio of height to diameter is preferably 1 to 2.2, more preferably 1.3 to 1.7. Common bottoms are dished, basket-arch and other curved bottoms, as well as conical bottoms. Examples of stirrer types are propeller, interprop, inclined blade or intermig stirrers. A number of stirring elements of 1 to 4, in particular 2 to 3, is preferred for the above containers.
In einer Ausführungsform wird die jeweilige Mischung nach der Dosierung des Verdickers (1) mindestens 15 Min., nach der Dosierung des Sulfopolymers (3) mindestens 10 Min., nach der Dosierung des Komplexbildners (4) mindestens 5 Min. und nach Dosierung des Tensids (2) mindestens 5 Min. gerührt.In one embodiment, the respective mixture is stirred for at least 15 minutes after the dosing of the thickener (1), for at least 10 minutes after the dosing of the sulfopolymer (3), for at least 5 minutes after the dosing of the complexing agent (4) and for at least 5 minutes after the dosing of the surfactant (2).
In einer Ausführungsform wird der mindestens eine Verdicker, bevorzugt mindestens ein Acrylat-(Co)polymer, in 1 bis 15 Gew.-%, bevorzugt 2,5 bis 10 Gew.-%, stärker bevorzugt 4 bis 7 Gew.-%, eingesetzt. In einer Ausführungsform wird das mindestens eine Tensid in 0,1 bis 10 Gew.-%, bevorzugt 1 bis 7 Gew.-%, stärker bevorzugt 2,5 bis 5 Gew.-%, eingesetzt. In einer Ausführungsform wird das mindestens eine Sulfopolymer in 0,1 bis 20 Gew.-%, bevorzugt 5 bis 17,5 Gew.-%, stärker bevorzugt 10 bis 15 Gew.-%, eingesetzt. In einer Ausführungsform wird der mindestens eine Komplexbildner in 1 bis 35 Gew.-%, bevorzugt 5 bis 35 Gew.-%, stärker bevorzugt 15 bis 30 Gew.-%, eingesetzt. In einer Ausführungsform wird Wasser in 5 bis 70 Gew.-%, bevorzugt 10 bis 55 Gew.-%, stärker bevorzugt 20 bis 45 Gew.-%, eingesetzt. Die Gew.-% sind dabei jeweils bezogen auf das Gesamtgewicht des Reinigungsmittels.In one embodiment, the at least one thickener, preferably at least one acrylate (co)polymer, is used in 1 to 15 wt.%, preferably 2.5 to 10 wt.%, more preferably 4 to 7 wt.%. In one embodiment, the at least one surfactant is used in 0.1 to 10 wt.%, preferably 1 to 7 wt.%, more preferably 2.5 to 5 wt.%. In one embodiment, the at least one sulfopolymer is used in 0.1 to 20 wt.%, preferably 5 to 17.5 wt.%, more preferably 10 to 15 wt.%. In one embodiment, the at least one complexing agent is used in 1 to 35 wt.%, preferably 5 to 35 wt.%, more preferably 15 to 30 wt.%. In one embodiment, water is used in 5 to 70 wt.%, preferably 10 to 55 wt.%, more preferably 20 to 45 wt.%. The weight percentages are based on the total weight of the cleaning agent.
In einer Ausführungsform ist ferner mindestens eine weitere Komponente ausgewählt aus anorganischen Salzen, Farbstoffen, Pigmenten, Konservierungsmitteln, pH-Stellmitteln, Strukturierungsmitteln, wie Sorbitol, Trehalose, Urea, Glycerin, 1,2-Propaniol, 1,3-Propandiol, Xylose, Xylitol, insbesondere Sorbitol, Parfümen und Enzymen enthalten.In one embodiment, at least one further component selected from inorganic salts, dyes, pigments, preservatives, pH adjusters, structuring agents, such as sorbitol, trehalose, urea, glycerin, 1,2-propaniol, 1,3-propanediol, xylose, xylitol, in particular sorbitol, perfumes and enzymes is also included.
Der pH-Wert der Zusammensetzung kann mittels üblicher pH-Stellmittel, beispielsweise Säuren wie Mineralsäuren oder organischen Säuren, wie z.B. Zitronensäure, und/oder Alkalien wie Natrium- oder Kaliumhydroxid, eingestellt werden, wobei - insbesondere bei gewünschter Handverträglichkeit - ein Bereich von 6 bis 10, bevorzugt von 6,5 bis 9, am stärksten bevorzugt von 7,0 bis 8,5, angestrebt ist.The pH of the composition can be adjusted by means of conventional pH adjusters, for example acids such as mineral acids or organic acids, such as citric acid, and/or alkalis such as sodium or potassium hydroxide, whereby - particularly if hand compatibility is desired - a range of 6 to 10, preferably 6.5 to 9, most preferably 7.0 to 8.5, is desired.
Zur Einstellung und/oder Stabilisierung des pH-Werts können der Zusammensetzung im erfindungsgemäßen Verfahren ein oder mehrere Puffer-Substanzen (INCI Buffering Agents) als pH-Stellmittel zugesetzt werden, üblicherweise in Mengen von 0,001 bis 5 Gew.-%, bevorzugt von 0,005 bis 3 Gew.-%, stärker bevorzugt von 0,01 bis 2 Gew.-%, noch stärker bevorzugt von 0,05 bis 1 Gew.-%, am stärksten bevorzugt 0,1 bis 0,5 Gew.-%, beispielsweise 0,2 Gew.-%. Bevorzugte Puffer-Substanzen sind die Zitronensäure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise Trinatriumcitrat·2 H2O und Trikaliumcitrat·H2O. Wie bereits oben beschrieben, haben die Citrate auch gleichzeitig eine Funktion als Komplexbildner. Falls der Einsatz von Citraten als Komplexbildner erfolgt, kann der Einsatz weiterer Puffersubstanzen obsolet sein.To adjust and/or stabilize the pH value, one or more buffer substances (INCI buffering agents) can be added to the composition in the process according to the invention as pH adjusters. are added, usually in amounts of 0.001 to 5 wt.%, preferably 0.005 to 3 wt.%, more preferably 0.01 to 2 wt.%, even more preferably 0.05 to 1 wt.%, most preferably 0.1 to 0.5 wt.%, for example 0.2 wt.%. Preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate·2 H 2 O and tripotassium citrate·H 2 O. As already described above, the citrates also function as complexing agents. If citrates are used as complexing agents, the use of other buffer substances may be obsolete.
Bevorzugt ist die mindestens eine weitere Komponente mindestens ein Enzym, stärker bevorzugt eine Protease. Die eingesetzten Proteasen sind bevorzugt alkalische Serin-Proteasen. Sie wirken als unspezifische Endopeptidasen, das heißt, sie hydrolysieren beliebige Säureamidbindungen, die im Inneren von Peptiden oder Proteinen liegen und bewirken dadurch den Abbau proteinhaltiger Anschmutzungen auf dem Reinigungsgut.Preferably, the at least one further component is at least one enzyme, more preferably a protease. The proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, i.e. they hydrolyze any acid amide bonds that are located inside peptides or proteins and thereby cause the degradation of protein-containing soiling on the items being cleaned.
Bei den erfindungsgemäß optional eingesetzten Proteasen handelt es sich bevorzugt um eine Serin-Protease, insbesondere um eine Subtilase, besonders bevorzugt um ein Subtilisin. Das Subtilisin kann dabei ein Wildtypenzym oder eine Subtilisin-Variante sein, wobei das Wildtypenzym bzw. das Ausgangsenzym der Variante bevorzugt aus einer der folgenden ausgewählt ist:
- der Alkalischen Protease aus Bacillus amyloliquefaciens (BPN'),
- der Alkalischen Protease aus Bacillus licheniformis (Subtilisin Carlsberg),
- der Alkalischen Protease PB92,
- Subtilisin 147 und/oder 309 (Savinase)
- der Alkalischen Protease aus Bacillus lentus, bevorzugt aus Bacillus lentus (DSM 5483),
- der Alkalischen Protease aus Bacillus alcalophilus (DSM 11233),
- der Alkalischen Protease aus Bacillus gibsonii (DSM 14391) oder einer hierzu mindestens zu 70% identischen Alkalischen Protease,
- der Alkalischen Protease aus Bacillus sp. (DSM 14390) oder einer hierzu mindestens zu 98,5% identischen Alkalischen Protease, und
- der Alkalischen Protease aus Bacillus sp. (DSM 14392) oder einer hierzu mindestens zu 98,1 % identischen Alkalischen Protease.
- the alkaline protease from Bacillus amyloliquefaciens (BPN'),
- the alkaline protease from Bacillus licheniformis (Subtilisin Carlsberg),
- the alkaline protease PB92,
- Subtilisin 147 and/or 309 (Savinase)
- the alkaline protease from Bacillus lentus, preferably from Bacillus lentus (DSM 5483),
- the alkaline protease from Bacillus alcalophilus (DSM 11233),
- the alkaline protease from Bacillus gibsonii (DSM 14391) or an alkaline protease that is at least 70% identical to it,
- the alkaline protease from Bacillus sp. (DSM 14390) or an alkaline protease that is at least 98.5% identical to it, and
- the alkaline protease from Bacillus sp. (DSM 14392) or an alkaline protease that is at least 98.1% identical.
Beispiele für die im erfindungsgemäßen Verfahren einsetzbaren Proteasen sind Subtilisin 309 oder funktionale Fragmente/Varianten davon und Varianten der Alkalischen Protease aus Bacillus lentus oder Varianten davon. Subtilisin 309 wird unter dem Handelsnamen Savinase® von der Firma Novozymes A/S, Bagsvaerd, Dänemark vertrieben. Von dem Subtilisin 309 aus Bacillus lentus sind unter den Handelsnamen Blaze® und Ovozyme® von der Firma Novozymes optimierte Enzymvarianten erhältlich, die eine bevorzugte Ausführungsform der Erfindung darstellen. Von der Alkalischen Protease aus Bacillus lentus DSM 5483 leiten sich beispielsweise die unter der Bezeichnung BLAP® geführten Protease-Varianten ab. Bevorzugt sind hier insbesondere solche Protease-Varianten, die gegenüber dem BLAP wt (Wildtyp) Enzym, in der Zählung gemäß BLAP wt, mindestens eine Mutation an R99 aufweisen, insbesondere R99E oder R99D, insbesondere bevorzugt ist R99E, sowie optional zusätzlich mindestens eine oder zwei, bevorzugt alle drei der Aminosäuresubstitutionen S3T, V4I und V199I aufweist, insbesondere bevorzugt sind die BLAP-Varianten, wie sie in SeqlD No 4 oder 5 der
In dem hier beschriebenen Verfahren können die als optionale Komponente einsetzbaren Enzyme ferner zusammen mit Begleitstoffen, etwa aus der Fermentation, konfektioniert sein. Bevorzugt werden die Enzyme als Enzymflüssigformulierung(en) eingesetzt.In the process described here, the enzymes that can be used as an optional component can also be packaged together with accompanying substances, for example from fermentation. The enzymes are preferably used as enzyme liquid formulation(s).
Die Proteasen werden in der Regel nicht in Form des reinen Proteins, sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder bevorzugt Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.The proteases are generally not provided in the form of pure protein, but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, preferably, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other additives.
Alternativ können die Enzyme verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem bevorzugt natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.Alternatively, the enzymes can be encapsulated, 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 enzymes are enclosed as if in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer that is impermeable to water, air and/or chemicals. In addition, other active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and are stable in storage due to the coating.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to package two or more enzymes together so that a single granulate has several enzyme activities.
Neben den Proteasen können auch weitere Enzyme, insbesondere Amylasen, Hemicellulasen, Cellulasen, Lipasen und Oxidoreduktasen zugesetzt werden.In addition to proteases, other enzymes, especially amylases, hemicellulases, cellulases, lipases and oxidoreductases, can also be added.
Bei der/den Amylase(n) handelt es sich bevorzugt um eine α-Amylase. Bei der Hemicellulase handelt es sich bevorzugt um eine β- Glucanase, eine Pektinase, eine Pullulanase und/oder eine Mannanase. Bei der Cellulase handelt es sich vorzugsweise um ein Cellulase-Gemisch oder eine Einkomponenten-Cellulase, bevorzugt bzw. überwiegend um eine Endoglucanase und/oder eine Cellobiohydrolase. Bei der Oxidoreduktase handelt es sich bevorzugt um eine Oxidase, insbesondere eine Cholin-Oxidase, oder um eine Perhydrolase. Die genannten Enzyme können alle wie oben für die Proteasen beschrieben konfektioniert sein.The amylase(s) is/are preferably an α-amylase. The hemicellulase is preferably a β-glucanase, a pectinase, a pullulanase and/or a mannanase. The cellulase is preferably a cellulase mixture or a single-component cellulase, preferably or predominantly an endoglucanase and/or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase. The enzymes mentioned can all be formulated as described above for the proteases.
In einer bevorzugten Ausführungsform umfasst die mindestens eine weitere Komponente eine Protease in einer Menge von 0,01 bis 1,6 Gew.-%, bevorzugt von 0,08 bis 1,2 Gew.-% bezogen auf das Gesamtgewicht der Zusammensetzung.In a preferred embodiment, the at least one further component comprises a protease in an amount of 0.01 to 1.6 wt.%, preferably 0.08 to 1.2 wt.%, based on the total weight of the composition.
In verschiedenen Ausführungsformen können das Enzym/die Enzyme mit Enzymstabilisatoren in einer Enzymzusammensetzung vorformuliert vorliegen. Das Enzym-Protein bildet dabei üblicherweise nur einen Bruchteil des Gesamtgewichts der Enzym-Zubereitung. Bevorzugt eingesetzte Enzymzubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, stärker bevorzugt zwischen 0,4 und 20 Gew.-% und am stärksten bevorzugt zwischen 0,8 und 10 Gew. % des Enzymproteins. In solchen Zusammensetzungen kann ein Enzymstabilisator in einer Menge von 0,05 bis 35 Gew.-%, bevorzugt von 0,05 bis 10 Gew.-%, bezogen auf das Gesamtgewicht in der Enzymzusammensetzung, enthalten sein. Diese Enzymzusammensetzung kann dann in dem erfindungsgemäßen Verfahren als Zusatzstoff zugesetzt werden und zwar in Mengen, die zu den oben angegeben Endkonzentrationen in der Zusammensetzung führen. Geeignete Enzymstabilisatoren sind im Stand der Technik bekannt. In verschiedenen Ausführungsformen können in dem erfindungsgemäßen Verfahren dementsprechend zusätzlich ein oder mehrere Enzymstabilisatoren zugesetzt werden.In various embodiments, the enzyme(s) can be preformulated with enzyme stabilizers in an enzyme composition. The enzyme protein usually only forms a fraction of the total weight of the enzyme preparation. Preferably used enzyme preparations contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and most preferably between 0.8 and 10% by weight of the enzyme protein. In such compositions, an enzyme stabilizer can be contained in an amount of 0.05 to 35% by weight, preferably from 0.05 to 10% by weight, based on the total weight in the enzyme composition. This enzyme composition can then be added as an additive in the process according to the invention in amounts that lead to the final concentrations in the composition specified above. Suitable enzyme stabilizers are known in the prior art. In various embodiments, one or more enzyme stabilizers can accordingly also be added in the process according to the invention.
Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren (Bicinchoninsäure; 2,2'-Bichinolyl-4,4'-dicarbonsäure) oder dem Biuret-Verfahren bestimmt werden. Die Bestimmung der Aktivproteinkonzentration erfolgt diesbezüglich über eine Titration der aktiven Zentren unter Verwendung eines geeigneten irreversiblen Inhibitors (für Proteasen beispielsweise Phenylmethylsulfonylfluorid (PMSF)) und Bestimmung der Restaktivität (vgl.
In einer Ausführungsform sind weniger als 5 Gew.-% an organischen Lösungsmitteln, basierend auf dem Gesamtgewicht des Reinigungsmittels enthalten. In einer bevorzugten Ausführungsform sind im Wesentlichen keine organischen Lösungsmittel enthalten. In einer Ausführungsform sind weniger als 6 Gew.-% an Verdickern, welche kein Acrylat-(Co)polymer sind, basierend auf dem Gesamtgewicht des Reinigungsmittels, enthalten. In einer bevorzugten Ausführungsform sind lediglich Acrylat-(Co)polymere als Verdicker enthalten.In one embodiment, less than 5% by weight of organic solvents are included, based on the total weight of the cleaning agent. In a preferred embodiment, essentially no organic solvents are included. In one embodiment, less than 6% by weight of thickeners that are not acrylate (co)polymers are included, based on the total weight of the cleaning agent. In a preferred embodiment, only acrylate (co)polymers are included as thickeners.
Ferner betrifft die Erfindung ein Reinigungsmittel, erhalten durch das Verfahren gemäß der vorliegenden Erfindung, wobei das Reinigungsmittel bevorzugt ein Geschirrspülmittel ist.Furthermore, the invention relates to a cleaning agent obtained by the process according to the present invention, wherein the cleaning agent is preferably a dishwashing agent.
In einem 11t Rührkessel wurden 3200 kg Wasser vorgelegt. Dann wurden 600 kg Acusol 810 als Verdicker dosiert und dabei wurde der Rührer mit 25% bzw. ca. 35 Upm gestartet. Anschließend kamen 1500 kg Sorbitol dazu, gefolgt von einem Sulfopolymer Acusol 590 mit 1300 kg und die Rührgeschwindigkeit wurde auf 29% bzw. ca. 40 Upm erhöht. Nachfolgend wurden 3000 kg Komplexbildner Trilon Ultimate hinzugefügt und dann noch 200 kg Wasser. Hierbei wurde die Drehgeschwindigkeit auf 50% bzw. ca. 70 Upm erhöht. Starke Schaumbildung trat wegen des Füllniveaus oberhalb des Rührblatts nicht auf. Dann wurden 400 kg Tensid (Dehypon E127) zugegeben. Final erfolgte die Dosierung von Zitronensäure und Enzymen. Das hergestellte Gel war nach 3 Wochen stabil.3200 kg of water were placed in an 11 t stirred tank. Then 600 kg of Acusol 810 were added as a thickener and the stirrer was started at 25% or approx. 35 rpm. Then 1500 kg of sorbitol were added, followed by a sulfopolymer Acusol 590 at 1300 kg and the stirring speed was increased to 29% or approx. 40 rpm. Then 3000 kg of complexing agent Trilon Ultimate were added and then another 200 kg of water. The rotation speed was increased to 50% or approx. 70 rpm. Heavy foaming did not occur due to the filling level above the stirring blade. Then 400 kg of surfactant (Dehypon E127) were added. Finally, citric acid and enzymes were added. The gel produced was stable after 3 weeks.
In einem 11t Rührkessel wurden 3200 kg Wasser vorgelegt und der Rührer wurde mit 25% bzw. ca. 35 Upm gestartet. Dann wurden 3000 kg Trilon Ultimate als Komplexbildner dosiert. Anschließend kamen 1500 kg Sorbitol dazu, gefolgt von einem Tensid (Dehypon E127), mit 400 kg und 200 kg Wasser. Dann wurde ein Sulfopolymer (Acusol 590) mit 1300 kg zugegeben. Nachfolgend wurden 600 kg Acusol 810 als Verdicker hinzugefügt. Final erfolgte die Dosierung von Zitronensäure und Enzymen. Das hergestellte Gel zeigte nach 3 Wochen eine Instabilität.3200 kg of water were placed in an 11 t stirred tank and the stirrer was started at 25% or about 35 rpm. Then 3000 kg of Trilon Ultimate were added as a complexing agent. Then 1500 kg of sorbitol were added, followed by a surfactant (Dehypon E127) with 400 kg and 200 kg of water. Then a sulfopolymer (Acusol 590) with 1300 kg was added. Then 600 kg of Acusol 810 was added as a thickener. Finally, citric acid and enzymes were added. The gel produced showed instability after 3 weeks.
Claims (13)
- A process for producing gel-like cleaning agents, comprising or consisting of the steps of:(i) placing water in a container which contains a stirring device, in particular a stirred tank;(ii) adding the cleaning agent components into the water, preferably by means of at least one metering pump, in particular by means of a metering pump, while stirring, in order to obtain a cleaning agent; wherein(1) at least one thickener selected from the group of polyacrylate (co)polymers,(2) at least one surfactant,(3) at least one sulfopolymer, and(4) at least one complexing agent are added, with the proviso that the components (1)-(4) are each added separately;
that the at least one thickener (1) is added before the at least one surfactant (2), the at least one sulfopolymer (3) and the at least one complexing agent (4); and the stirring speed is constant or increased at each addition, but is increased at least once after the first addition. - The process according to claim 1, wherein(i) all components are added sequentially; and/or(ii) after each second component, the stirring speed is increased up to the maximum speed by 5 to 75% in each case, starting from the previous stirring speed, more preferably wherein, after each component, the stirring speed is increased by 5 to 40%, starting from the previous stirring speed; and/or(iii) the at least one thickener is added before the at least one surfactant (2), the at least one sulfopolymer (3) and the at least one complexing agent (4), and at least one further component, which is different from these components, or water is added between the addition of the at least one thickener (1) and one or more of the components (2)-(4).
- The process according to one of the preceding claims, wherein(a) the at least one surfactant (2) comprises a surfactant from the group of hydroxy mixed ethers;(b) the at least one sulfopolymer (3) is a polymer from the group of the acrylate copolymers, preferably containing acrylamidopropanesulfonic acid units;(c) the at least one complexing agent (4) is selected from organic complexing agents, preferably from aminocarboxylic acids and the salts thereof, more preferably from MGDA and GLDA and the salts thereof.
- The process according to one of the preceding claims, wherein(a) the at least one surfactant (2) comprises a surfactant from the group of hydroxy mixed ethers;(b) the at least one sulfopolymer (3) is a polymer from the group of the acrylate copolymers, preferably containing acrylamidopropanesulfonic acid units;(c) the at least one complexing agent (4) is selected from citric acid and the salts thereof, preferably trisodium citrate.
- The process according to one of the preceding claims,
characterized in that the sequence of the addition of the components (1)-(4) takes place in such a way that component (1) is added first, then component (3), then component (4), and then component (2), wherein preferably at least one further component, which is different from these components, particularly preferably a structuring agent, in particular sorbitol, or water is added between the addition of the at least one thickener (1) and the component (3). - The process according to one of the preceding claims,
characterized in that the initial stirring speed is 30 rpm, preferably 35 rpm, and/or the stirring speed is 80 rpm, preferably 70 rpm, when the final component is added. - The process according to one of the preceding claims, wherein a dynamic mixer is additionally used for stirring.
- The process according to one of the preceding claims, wherein the container fill level before the metering of the thickener (1) is approximately 30%, before the metering of the sulfopolymer (3) is approximately 47%, before the metering of the complexing agent (4) is approximately 63%, and before the metering of the surfactant (2) is approximately 88%, based on the volume of the container.
- The process according to one of the preceding claims, wherein the corresponding mixture after metering of the thickener (1) is stirred for at least 15 min, after the metering of the sulfopolymer (3) for at least 10 min, after the metering of the complexing agent (4) for at least 5 min, and after metering of the surfactant (2) for at least 5 min.
- The process according to one of the preceding claims, whereinthe at least one thickener, preferably at least one acrylate (co)polymer, is used in 1 to 15 wt.%, preferably 2.5 to 10 wt.%, more preferably 4 to 7 wt.%; and/or the at least one surfactant is used in 0.1 to 10 wt.%, preferably 1 to 7 wt.%, more preferably 2.5 to 5 wt.%; and/orthe at least one sulfopolymer is used in 0.1 to 20 wt.%, preferably 5 to 17.5 wt.%, more preferably 10 to 15 wt.%; and/orthe at least one complexing agent is used in 1 to 35 wt.%, preferably 5 to 35 wt.%, more preferably 15 to 30 wt.%; and/orwater is used in 5 to 70 wt.%, preferably 10 to 55 wt.%, more preferably 20 to 45 wt.%;in each case based on the total weight of the cleaning agent.
- The process according to one of the preceding claims, wherein at least one further component selected from inorganic salts, dyes, pigments, preservatives, pH adjusters, structuring agents, perfumes and enzymes is also contained.
- The process according to one of the preceding claims, wherein(a) less than 5 wt.% of organic solvents are contained, based on the total weight of the cleaning agent, and/or(b) less than 6 wt.% of thickeners which are not an acrylate (co)polymer are contained, based on the total weight of the cleaning agent.
- A gel-like cleaning agent obtained by the process according to one of claims 1 to 12, wherein the cleaning agent is preferably a dishwasher detergent.
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EP2621463A2 (en) * | 2010-09-30 | 2013-08-07 | Lubrizol Advanced Materials, Inc. | Structured acrylate copolymer for use in multi-phase systems |
DE102012202176A1 (en) * | 2012-02-14 | 2013-08-14 | Henkel Ag & Co. Kgaa | Sulfopolymer-containing liquid detergent with low water content |
DE102012222266A1 (en) * | 2012-12-05 | 2014-06-05 | Henkel Ag & Co. Kgaa | Process for the preparation of low-water to anhydrous liquid washing or cleaning agents |
DE102012222267A1 (en) * | 2012-12-05 | 2014-06-05 | Henkel Ag & Co. Kgaa | Low-water to anhydrous liquid detergents |
DE102013207933A1 (en) | 2013-04-30 | 2014-10-30 | Henkel Ag & Co. Kgaa | Detergent containing proteases |
DE102013225584A1 (en) | 2013-12-11 | 2015-06-11 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent containing N-based complexing agents |
DE102013226301A1 (en) * | 2013-12-17 | 2015-06-18 | Henkel Ag & Co. Kgaa | Liquid dishwashing detergent with optimized viscosity |
DE102015206485A1 (en) | 2015-04-10 | 2016-10-13 | Henkel Ag & Co. Kgaa | Dishwashing detergent containing nitrogen-based complexing agents and MGDA |
DE102015213938A1 (en) | 2015-07-23 | 2017-01-26 | Henkel Ag & Co. Kgaa | Use of a combination of complexing agent and surfactant to improve the rinse performance |
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