DE102020132593A1 - Gradual addition of thickeners in the manufacture of detergents and cleaning agents to improve processability - Google Patents

Abstract

The present invention relates to a specific process for the production of detergents and cleaning agents and a detergent or cleaning agent obtained by the process.

Description

The present invention relates to a specific process for the production of detergents and cleaning agents and a detergent or cleaning agent obtained by the process.

In the field of detergents and cleaning agents, in particular liquid detergents and cleaning agents, such as gel-like detergents and cleaning agents, setting a target viscosity and/or generating a yield point is important in order not only to have a visually appealing, but also a user-friendly, i.e. to provide an easy-to-handle end product for the consumer. Thickeners are used for this purpose. Depending on the thickener, the addition position during the manufacture of the respective agent is important. Swelling thickeners (systems), such as xanthan gum, develop their best effect when they are dosed in plenty of free water, i.e. usually at the beginning of the detergent or cleaning agent manufacturing process. If a thickener is added at the beginning of the manufacturing process, the viscosity initially increases extremely and is only reduced to the target value by adding other ingredients such as surfactants, polymers, complexing agents, etc. An initially high viscosity makes it difficult overall to process the agent. On the one hand, it may be necessary to use larger and more powerful machines, on the other hand, the energy expenditure increases in order to be able to process and ultimately produce a corresponding agent. In general, customers want an agent with a low viscosity despite a high yield point in order to stabilize the particles contained in the agent.

The object of the present invention was therefore to provide a process for the production of detergents and cleaning agents which overcomes the above-described disadvantages of conventional production processes and enables energy-saving and machine-friendly detergent or cleaning agent production.

The inventors of the present invention have surprisingly found that this problem can be solved by a production process in which the detergent components are added in a specific order. A first amount of thickener must be added before the other washing or cleaning agent components, whereupon a second amount of thickener is then metered in.

• (i) Dosieren einer ersten Menge an Verdicker in eine wässrige Lösung oder in Wasser;
• (ii) optional Vermischen der nach Schritt (i) erhaltenen Mischung;
• (iii) Dosieren einer oder mehrerer weiterer Wasch- oder Reinigungsmittelkomponenten in die so erhaltene Mischung;
• (iv) optional Vermischen der nach Schritt (iii) erhaltenen Mischung; und
• (v) Dosieren einer zweiten Menge an Verdicker in die so erhaltene Mischung.

In a first aspect, the invention therefore relates to a process for the production of detergents and cleaning agents, comprising the following steps:

• (i) metering a first amount of thickener into an aqueous solution or into water;
• (ii) optionally mixing the mixture obtained after step (i);
• (iii) dosing of one or more further washing or cleaning agent components into the mixture thus obtained;
• (iv) optionally mixing the mixture obtained after step (iii); and
• (v) metering a second quantity of thickener into the mixture thus obtained.

In a second aspect, the invention relates to a washing or cleaning agent obtained by the method according to the present invention.

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. Each feature 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 should 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.

"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 specification 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 giving information about the amount of the individual compounds.

Unless otherwise stated, all percentages are by weight, based in each case on the total weight of the corresponding composition. Numeric ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.

Unless otherwise stated, all quantitative data given in connection with the compositions described herein relate to % by weight in each case based on the total weight of the composition. Furthermore, such amounts, which relate to at least one component, always relate to the total amount of this type of component contained in the composition, unless explicitly stated otherwise. This means that such amounts, for example in connection with “at least one thickener”, relate to the total amount of thickeners contained in the composition, unless explicitly stated otherwise.

Numerical values given herein without decimal places refer to the full stated value with one decimal place. For example, "99%" means "99.0%".

The expression “approximately” 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%.

The expression "substantially free from" means that the respective compound can in principle be present, 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 “substantially free from” of a specific compound is therefore preferably 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 the composition.

Numeric ranges specified in the format "in/from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.

Information about the molecular weight relates 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.

"Liquid" as used in the context of the present invention means all flowable compositions (at 20°C, 1.013 bar), including gels and paste-like compositions, as well as non-Newtonian liquids that exhibit a yield point.

Gel or gel-like compositions or agents within the meaning of the present invention are those which have a viscosity of 50 to 5000 mPas, preferably 100 to 4800 mPas. The viscosity can be determined with a Brookfield LVDV II+ laboratory viscometer at 20° C. using spindle 31 and 3 or 6 rpm.

• (i) Dosieren einer ersten Menge an Verdicker in eine wässrige Lösung oder in Wasser;
• (ii) optional Vermischen der nach Schritt (i) erhaltenen Mischung;
• (iii) Dosieren einer oder mehrerer weiterer Wasch- oder Reinigungsmittelkomponenten in die so erhaltene Mischung;
• (iv) optional Vermischen der nach Schritt (iii) erhaltenen Mischung; und
• (v) Dosieren einer zweiten Menge an Verdicker in die so erhaltene Mischung.

The invention relates to a process for the production of detergents and cleaning agents, comprising the following steps:

• (i) metering a first amount of thickener into an aqueous solution or into water;
• (ii) optionally mixing the mixture obtained after step (i);
• (iii) dosing of one or more further washing or cleaning agent components into the mixture thus obtained;
• (iv) optionally mixing the mixture obtained after step (iii); and
• (v) metering a second quantity of thickener into the mixture thus obtained.

The manner in which the respective components are dosed is not limited to any specific methodology and can be done in the conventional manner. The same applies to the mixing, for example stirring, of the mixture obtained in each case. Mixing enables the metered components to be distributed as evenly as possible in the respective mixture. Static but also dynamic stirrers can be used. In one embodiment, the stirrer is located below the liquid surface in the container. Suitable stirred tanks can have volumes of 10 to 500,000 liters. The height to diameter ratio may be 1 to 2.2, more preferably 1.3 to 1.7. Common floors are dished, basket arch and other curved floors, as well as conical floors. Exemplary stirrer types are propeller, interprop, pitched blade or intermig stirrers. A number of stirring elements of 1 to 4, in particular 2 to 3, is preferred for the above containers. Stirring speeds can be freely selected and adjusted to the consistency of the respective mixture. Exemplary stirring speeds are in the range of about 10 rpm to 150 rpm, for example in the range of 20 rpm to 100 rpm. Stirring speeds can be freely varied and adjusted during the process. For example, an initial slow stirring rate can be increased once or in increments. Likewise, an initial high stirring speed can be reduced once or gradually. Furthermore, it is possible to apply alternating stirring speeds in the course of the production process according to the invention. Stirring times can also vary and can be adjusted, but will typically be in the range of about 1 minute to about 5 hours, for example about 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 45, or 60 minutes , 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 hours. Under certain circumstances, it may be useful to continue the mixing process for a certain period of time, as defined above, after the components have been metered in, so that the desired viscosity can be established. This applies, for example, to some swelling thickeners such as xanthan gum.

The thickener or thickeners which is/are metered in at least in steps (i) and (v) of the process according to the invention can each be identical. It is also possible to dose different types of thickeners in the respective steps.

Substances which are usually used as thickeners in detergents or cleaning agents are known in the prior art and the present invention is not limited to the metering of a specific type of thickener.

Polymeric thickeners which can be used according to the invention are the polyelectrolytes which have a thickening effect, polycarboxylates, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers.

Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacant, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used as an alternative, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl -, Hydroxypropylmethyl- or Hydroxyethyl-methylcellulose or cellulose acetate.

A preferred polymeric thickening agent is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15×10 ⁶ and is available, for example, from Kelco under the trade name Keltrol®. for example as a cream-colored powder Keltrol® T (Transparent) or as white granules Keltrol® RD (Readily Dispersable).

Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI: carbomer), which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from BFGoodrich under the trade name Carbopol®, for example Carbopol® 940 (molecular weight M _w approx. 4,000,000 g/mol), Carbopol® 941 (molecular weight M _w approx. 1,250,000 g/mol) or Carbopol® 934 (molecular weight M _w approx. 3,000,000 g/mol).

However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters, preferably formed with C _1-4 alkanols (INCI: acrylates copolymer). which include the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which, for example, from Rohm & Haas under the trade names Aculyn® and Acusol® are available, for example the anionic non-associative polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, which include, for example, the copolymers crosslinked with an allyl ether of sucrose or pentaerythritol of C _10-30 -alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 -Alkanols formed, esters (INCI Acrylates/C _10-30 Alkyl Acrylate Crosspolymer) belong and which are available, for example, from BFGoodrich under the trade name Carbopol®, for example the hydrophobic Carbopol® ETD2623 and Carbopol® 1382 (INCI: Acrylates/C _10-30 Alkyl Acrylate Crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® EX 473).

In various embodiments, one or more thickeners from the group of polyacrylate (co)polymers are preferably used. All polyacrylate (co)polymers known to the person skilled in the art which have a thickening effect for achieving gels are suitable here. For example, such polymers are available under the trade name Acusol from Dow Corning Inc. Acusol 810 and 820 are particularly suitable 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 using 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 1.049 g/cm ³ .

In various embodiments, the ratio of the first amount of thickener (dosed according to step (i) of the method according to the invention) and the second amount of thickener (dosed according to step (v) of the method according to the invention) is in the range from 5:1 to 1:1 and is approximately 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1 or 1:1. In some preferred embodiments, the ratio of the first amount of thickener and the second amount of thickener is about 1:1.

In further embodiments, the total amount of metered thickener in the washing or cleaning agent is in the range from about 0.1 to about 2.0% by weight, for example about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1, 7, 1.8, 1.9 or 2.0% by weight, more preferably in the range from about 0.2 to about 1.5% by weight, most preferably in the range from about 0.5 to about 0, 7% by weight, based in each case on the total weight of the detergent or cleaning agent.

It can be preferred if the manufacturing process comprises, in addition to the aforementioned steps (i)-(v), at least one further step (vi) of dosing one or more additional detergent or cleaning agent components into the mixture obtained after step (v). Accordingly, in some embodiments, a method according to the invention can comprise one or more, for example two or three, further steps (vi), which provide for the dosing of at least one further detergent or cleaning agent component. It is also provided that, following step (vi), the mixture obtained in this way is mixed, for example stirred, in order to ensure the most uniform possible distribution of the metered-in components in the respective mixture.

In various embodiments, the ratio of the amount of detergent or cleaning agent component(s) metered in according to step (iii) and the amount of detergent or cleaning agent component(s) metered in according to step (vi) is in the range of approximately 100:1 to 1:1 and is approximately 100:1, 95:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50: 1, 45:1, 40:1, 35:1, 30:1, 25:1, 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1 or 1: 1.

Furthermore, it is provided that further amounts of thickener can be metered in after step (v) and/or one or more steps (vi) of the mixture obtained in each case. Further amounts of thickener can be metered in, for example, in one or more steps, for example two or three steps. However, the majority of the components to be metered into the agent are preferably metered in in steps (i)-(v) of the method according to the invention. Of course, the metering of a further amount of thickener (in addition to the amounts metered according to step (i) and (v)) can also precede and/or follow a mixing step as defined and described herein. In general, it is accordingly not provided that the final amount of thickener is added at the last position in the manufacturing process, but a final metering of thickener as late as possible is clearly recommended, since otherwise the advantageous effect to be achieved as desired will not be achieved in contrast to a single metering at the beginning of the manufacturing process would be lost or unnecessarily weakened. As was surprisingly found, the addition of a second amount of thickener, as defined and described herein, further increases both the viscosity and yield point of the mixture. Depending on the amount of thickener which is metered in according to steps (i) and (v) of the process according to the invention, both variables can be adjusted. In some embodiments, it is further provided that the viscosity of an agent produced according to the invention matures to the target value over a period of several days up to several weeks. In particular, the method according to the invention enables the setting of viscosity and flow point largely independently of one another, and in particular also the setting of a low flow point despite high viscosity. Another advantage is that no additives are needed for thickener premixes.

According to the invention, the first amount of thickener, as defined above, is metered either into water or into an aqueous solution. The term "water" as used in the context of the present invention includes both tap water and demineralized water. In various embodiments, however, the first amount of thickener is metered into an aqueous solution, preferably into an aqueous solution of at least one salt.

In principle, both inorganic and organic salts are suitable. However, according to step (i) of the method according to the invention, an aqueous solution of a salt is preferably used, the water-soluble salt, ie the one salt or else a mixture of salts, in particular being a salt or salts which and detergents are usually added to lower the viscosity. These can be inorganic and/or organic salts. In some embodiments it is one or more inorganic salts.

Inorganic salts that can be used according to the invention are preferably selected from the group consisting of colorless, water-soluble halides, sulfates, sulfites, carbonates, hydrogen carbonates, nitrates, nitrites, phosphates and/or oxides of alkali metals, alkaline earth metals, aluminum and/or transition metals; ammonium salts can also be used. Halides and sulfates of the alkali metals are particularly preferred; the inorganic salt is therefore preferably selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. Sodium chloride is particularly preferred.

The organic salts that can be used according to the invention are, in particular, colorless, water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and/or transition metal salts of carboxylic acids, including dicarboxylic acids. The salts are preferably selected from the group consisting of formate, acetate, propionate, citrate, malate, maleate, tartrate, succinate, malonate, oxalate, lactate, fumarate, adipate, succinate, glutarate, methylglycine diacetic acid trisodium salt and mixtures thereof.

In various embodiments, the salt concentration in the aqueous solution to which the first amount of thickener is metered according to step (i) of the method of the invention is in the range from about 0.1% to about 1.0%, more preferably in the range from about 0. 2% to about 0.8%, more preferably in the range from about 0.2% to about 0.5%, for example about 0.3%.

The one or more detergent or cleaning agent components metered in according to step (iii) and optionally step (vi) are detergent and cleaning agent components that are already known in the prior art and will be known in the future. In various embodiments is / are the one or more detergent or cleaning agent components according to step (iii) and optionally step (vi) selected from the group consisting of surfactants, enzymes, bleaches, complexing agents, builders, electrolytes, non-aqueous solvents, pH adjusters , fragrances, fragrance carriers, skin care products, fluorescent agents, dyes, pigments, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobic and impregnating agents , plasticizing components and UV absorbers, but not limited to these.

Surfactants suitable in the context of the present invention include all surfactants commonly used for this purpose but hereafter known. Suitable surfactants are cationic, anionic, nonionic or zwitterionic surfactants or mixtures thereof. Anionic and/or nonionic surfactants are preferred. For example, surfactants selected from alkyl benzene sulfonates, alkyl sulfates, alkyl ester sulfonates, secondary alkane sulfonates, 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. Fatty alcohol alkoxylates are particularly preferred, more preferably fatty alcohol ethoxylates or propoxylates or their mixed ethers, in particular with a fatty alcohol carbon chain length 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.

Polymers suitable as additives are in particular maleic acid-acrylic acid copolymer Na salt (for example the commercially available Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example the commercially available Sokalan® CP 10 of BASF, Ludwigshafen (Germany)), modified polycarboxylate sodium salt (for example the commercially available Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example the commercially available Silwet® L-77 from the company BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example the commercially available Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide/propylene oxide segments (polyether blocks)), preferably water-soluble linear polyethersiloxanes with terminal polyether blocks such as the commercially available compounds Tegopren® 5840, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 from Evonik, Essen (Germany). In some embodiments of the invention, the polymers mentioned are omitted.

Furthermore, sulfopolymers can be added. All sulfopolymers known to those skilled in the art which can be used in cleaning agents are suitable as sulfopolymers. 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 is/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 represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or for -COOH or -COOR ⁴ where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

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. Of course, the unsaturated dicarboxylic acids can also be used.

The monomers containing sulfonic acid groups are those of the formula R ⁵ (R ⁶ )C=C(R ⁷ )-X-SO ₃ H
preferably, in which R ⁵ to R ⁷ independently 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, with - NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals or -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 is 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 -.

Preferred among these monomers are those of the formulas _H2C =CH-X- _SO3H 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 is 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 -.

Particularly preferred sulfonic acid group-containing monomers 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-hydroxy-propanesulfonic 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 the polymers, some or all of the sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular sodium ions. The use of 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 in the case of copolymers which only contain carboxylic acid group-containing monomers and sulfonic acid group-containing monomers is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight; the monomers are preferably selected from those mentioned above.

The molar mass of the sulfo-copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired application. Preferred copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

For example, such polymers are available under the trade name Acusol from Dow Corning Inc., Acusol 590 or Acusol 588 being particularly suitable.

Enzymes suitable for use in the context of the present invention are also known in the art and include proteases, amylases, hemicellulases, cellulases, lipases and oxidoreductases.

At least one protease is preferably metered in. The proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, which means that they hydrolyze any acid amide bonds that are inside peptides or proteins, thereby breaking down protein-containing soiling on the items to be cleaned.

• - 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 proteases optionally used according to the invention are preferably a serine protease, in particular a subtilase, particularly preferably a subtilisin. The subtilisin can be a wild-type enzyme or a subtilisin variant, with the wild-type enzyme or the starting enzyme of the variant preferably being selected from one of the following:

• - 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 thereto,
• - the alkaline protease from Bacillus sp. (DSM 14390) or an alkaline protease which is at least 98.5% identical thereto, and
• - the alkaline protease from Bacillus sp. (DSM 14392) or an alkaline protease which is at least 98.1% identical thereto.

Examples of the proteases that can be used in the method 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 marketed under the trade name Savinase® by Novozymes A/S, Bagsvaerd, Denmark. Optimized enzyme variants of the subtilisin 309 from Bacillus lentus are available under the trade names Blaze® and Ovozyme® from the company Novozymes, which represent a preferred embodiment of the invention. For example, the protease variants listed under the name BLAP® are derived from the alkaline protease from Bacillus lentus DSM 5483. Preference is given here in particular to those protease variants which, compared to the BLAP wt (wild-type) enzyme, counted according to BLAP wt, have at least one mutation on R99, in particular R99E or R99D, R99E being particularly preferred, and optionally at least one or two in addition , preferably all three of the amino acid substitutions S3T, V4I and V199I, particularly preferred are the BLAP variants, as in SeqID No. 4 or 5 of WO2014/177430 are described.

In the process described here, the enzymes that can be used as optional components can also be packaged together with accompanying substances, for example from the fermentation. The enzymes are preferably used as enzyme liquid formulation(s).

As a rule, the proteases are not provided in the form of the pure protein, but rather in the form of stabilized preparations that can be stored and transported. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or preferably solutions of the enzymes, advantageously as concentrated as possible, with a low water content and/or containing stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated, for example by spray drying or extruding the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as in a set gel 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 substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. beneficial Advantageously, such granules, for example due to the application of polymeric film formers, produce little dust and are stable on storage due to the coating.

Furthermore, it is possible to formulate two or more enzymes together, so that a single granulate has several enzyme activities.

In addition to the proteases, other enzymes, in particular amylases, hemicellulases, cellulases, lipases and oxidoreductases can also be added.

The amylase(s) is 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 one-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 various embodiments, an enzyme or an enzyme mixture, preferably a protease or an enzyme mixture containing a protease, is used in an amount of from 0.01 to 3.5% by weight, preferably from 0.08 to 2.8% by weight. based on the total weight of the composition metered.

In various embodiments, the enzyme(s) may be pre-formulated with enzyme stabilizers in an enzyme composition. The enzyme protein usually makes up only 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 enzyme protein. In such compositions, an enzyme stabilizer can be included in an amount of 0.05 to 35% by weight, preferably 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 which lead to the final concentrations in the composition indicated above. Suitable enzyme stabilizers are known in the art. In various embodiments, accordingly, one or more enzyme stabilizers can also be added in the method 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. In this regard, the active protein concentration is determined via a titration of the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88 , 24 (1966), pp. 5890-5913).

Furthermore, non-aqueous solvents can be added to the agents to be produced according to the invention. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these Solvent.

The one or more non-aqueous solvent(s) is/are usually present in an amount of from 0.1% to 60%, preferably from 5% to 60%, more preferably from 10% to 30% by weight based on the total weight of the composition , contain. In one embodiment, a detergent or cleaning agent produced according to the invention preferably contains less than 5% by weight of organic solvents, based on the total weight of the detergent or cleaning agent. In a preferred embodiment, essentially no organic solvents are present.

Builders which are suitable for use in the context of the present invention include all builders known in the art and known in the future, i.e. water-soluble and/or water-insoluble, organic and/or inorganic builders.

The builders that can generally be used include, in particular, the aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co)builders and—where there are no ecological prejudices against their use—also the phos phate. According to preferred embodiments, however, the agents according to the invention are phosphate-free.

In one embodiment, the complexing agents are selected from the group of aminocarboxylic acids and their salts, for example methylglycine diacetic acid (MGDA) or its salts, glutamic diacetic acid (GLDA) or its salts, ethylene diamine diacetic acid or its salts (EDDS) or mixtures thereof. Other suitable complexing agents are, for example, in DE 102015206485 A1 , EP 3080236 A1 or DE 102015213938 A1 described. A suitable commercially available complexing agent is available, for example, under the trade name Trilon Ultimate 2L from BASF AG.

In a further embodiment, the complexing agent is selected from citric acid and the salts of citric acid. The at least one complexing agent is preferably trisodium citrate. In cases where citric acid or one of its salts is used as a complexing agent, it can also act as a pH adjuster and/or buffer substance. A further addition of a separate pH adjuster or a buffer substance can then be dispensed with. In such cases, the specified quantity limits for the complexing agent then apply to the total quantity of the specified compound in the composition, regardless of the function.

The content of such complexing agents or their salts can be, for example, between 0.1 and 40% by weight, preferably between 1 and 30% by weight and in particular between 5 and 25% by weight, based in each case on the total weight of the detergent or detergent. Combinations of various of the aforementioned complexing agents are also possible and provided.

In various embodiments, the at least one builder is selected from the group consisting of methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), and 1-hydroxyethane-1,1-diphosphonate (HEDP).

In general, the pH of the agents can be adjusted using standard pH regulators. In various embodiments, the pH of corresponding agents is in a range from 6.5 to 12, preferably 7.0 to 11.5, preferably greater than 7, in particular 7.5 to 10.5.

Acids and/or alkalis are used as pH adjusters. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide is preferred. Even if volatile alkali, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule, can be used to adjust the pH, the alkanolamine can here be selected from the group consisting of mono -, Di-, triethanol- and -propanolamine and mixtures thereof, such volatile alkali sources, in particular ethanolamines, are preferably avoided. In various embodiments, the agents according to the invention therefore contain less than 1.75% by weight of alkanolamine, in particular monoethanolamine, and they are very particularly preferably free of it.

To adjust and/or stabilize the pH, an agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2H ₂ O and tripotassium citrate H ₂ O.

In various embodiments, at least one pH adjuster is metered in in step (iii). In various embodiments, at least one acid is metered in in step (iii). The addition of an acid causes the pH of the respective mixture to decrease, which can result in an increase in viscosity. Accordingly, in some embodiments it is provided that the metering of the second amount of thickener takes place after the pH value has been adjusted, in particular after the addition of an acid. Accordingly, in some embodiments, in particular in embodiments in which a pH adjuster, in particular an acid, is metered in in step (iii), no thickener is metered in in step (iii) of the method according to the invention and/or that in Step (vi), if part of the process according to the invention, no pH adjuster, in particular no acid, is metered in.

In some embodiments, the at least one thickener is present in a total amount of about 0.2 to 1.5% by weight, preferably 0.3 to 1.0% by weight, more preferably 0.5 to 0.7% by weight. %, dosed. In some embodiments, at least one surfactant is further enhanced in an amount of about 0.1% to 10% by weight, preferably 1% to 7% by weight preferably 2.5 to 5% by weight; and/or at least one complexing agent in an amount of about 1 to 35% by weight, preferably 5 to 35% by weight, more preferably 15 to 30% by weight and/or at least one enzyme in an amount of about 0 0.01 to 3.5% by weight, more preferably 0.08 to 2.8% by weight, more preferably 0.08 to 1.2% by weight and/or at least one pH adjuster, preferably at least one acid dosed in an amount of from about 0.1 to about 10% by weight, more preferably 0.3 to 5% by weight, more preferably 0.5 to 5% by weight and/or at least one sulfopolymer in an amount from about 0.1 to 20% by weight, preferably 5 to 17.5% by weight, more preferably 10 to 15% by weight. The water content of a composition produced according to the invention is, in some embodiments, approximately 5 to 70% by weight, preferably 10 to 55% by weight, more preferably 20 to 45% by weight. The % by weight are in each case based on the total weight of the cleaning agent.

Accordingly, the invention also relates to a washing or cleaning agent produced in a method according to the present invention. In various embodiments, such a washing or cleaning agent is a liquid washing or cleaning agent, preferably a washing or cleaning agent in gel form. In various embodiments, a washing or cleaning agent produced according to the invention has a viscosity of 50 to 5000 mPas, preferably 100 to 4800 mPas. In various embodiments, a detergent produced according to the invention is a dishwashing detergent, for example a hand dishwashing detergent. In various other embodiments, an agent produced according to the invention is a detergent.

examples

Example according to the invention:

A dishwashing detergent is prepared in a stirred tank with a volume of 10 m ³ . The container has a 3-stage Intermig stirrer. Water is presented with 5530 L. The stirring speed is started at 40 rpm. An alkaline earth metal salt, optionally potassium chloride, is then metered in at 3% and the mixture is stirred for 10 minutes. Then xanthan gum is added at 0.35%. The mixture is then stirred until the thickener is dissolved. In the following steps, 10% Acusol 588, 10% trisodium citrate, 10% Trilon Ultimate, 1% preservative, 3% citric acid anhydrate and 5% Dehypon E127 are added. Now the stirrer speed is increased to 60 rpm and another 0.35% xanthan gum is added. Finally, 2% Savinase is added.

Comparative example 1:

5530 l of water are placed in a stirred tank with a volume of 10 m ³ and a 3-stage Intermig stirrer. The stirring speed is adjusted to 40 rpm. Now dosing of 3% potassium chloride takes place. Then 0.7% xanthan gum is added. The stirrer power is limited and due to the very high viscosity, the thickener does not mix completely. Manufacturing is canceled.

Comparative example 2:

5530 l of water are metered into a 10 m ³ stirred tank with a 3-stage Intermig stirrer. The stirring speed is adjusted to 40 rpm. In addition to 3% potassium chloride, 0.7% xanthan gum is also added. The stirrer power is increased to ensure thorough mixing. In the following steps, 10% Acusol 588 and 10% trisodium citrate are added. Due to the high viscosity, the mixing time is significantly longer. Then 10% Trilon Ultimate, 1% preservative, 3% citric acid anhydrate and 5% Dehypon E127 are also dosed. Finally, 2% Savinase is added.

QUOTES INCLUDED IN DESCRIPTION

This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• WO 2014/177430 [0053]
• DE 102015206485 A1 [0067]
• EP 3080236 A1 [0067]
• DE 102015213938 A1 [0067]

Claims (13)

Process for the production of detergents and cleaning agents, comprising the following steps: (i) metering a first amount of thickener into an aqueous solution or into water; (ii) optionally mixing the mixture obtained after step (i); (iii) dosing of one or more further washing or cleaning agent components into the mixture thus obtained; (iv) optionally mixing the mixture obtained after step (iii); and (v) metering a second quantity of thickener into the mixture thus obtained. The procedure according to claim 1 , characterized in that the ratio of the first amount of thickener and the second amount of thickener is in the range of 5:1 to 1:1. The procedure according to claim 1 or claim 2 , characterized in that the total amount of thickener dosed in the detergent or cleaning agent is in the range from about 0.1 to about 2.0% by weight, more preferably in the range from about 0.2 to about 1.5% by weight , most preferably in the range from about 0.5 to about 0.7% by weight, based in each case on the total weight of the detergent or cleaning agent. The method according to any one of the preceding claims, characterized in that the method comprises at least one further step (vi) of dosing one or more additional detergent or cleaning agent components into the mixture obtained after step (v). The procedure according to claim 4 , characterized in that the ratio of the amount of detergent or cleaning agent component(s) metered in according to step (iii) and the amount of detergent or cleaning agent component(s) metered in according to step (vi) is in the range of 100:1 up to 1:1. The method according to any one of the preceding claims, characterized in that the first amount of thickener according to step (i) is metered into an aqueous solution of at least one salt. The method according to any one of the preceding claims, characterized in that the one or more detergent or cleaning agent components according to step (iii) and optionally step (vi) are selected from the group consisting of surfactants, enzymes, bleaching agents, complexing agents, builders, electrolytes , non-aqueous solvents, pH adjusters, fragrances, fragrance carriers, skin care products, fluorescent agents, dyes, pigments, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, bittering agents , ironing aids, repellents and impregnating agents, softening components and UV absorbers. The method according to any one of the preceding claims, characterized in that at least one pH adjusting agent is metered in in step (iii). The method according to any one of the preceding claims, characterized in that no thickener is metered in in step (iii). The method according to one of Claims 4 until 9 , characterized in that no acid is metered in in step (vi). Detergents or cleaning agents obtained by the process according to any one of Claims 1 until 10 . The detergent or cleaning agent according to claim 11 , characterized in that the washing or cleaning agent is liquid. The detergent or cleaning agent according to claim 11 or claim 12 , characterized in that it has a viscosity of 50 to 5000 mPas, preferably 100 to 4800 mPas.