EP2958984A1

EP2958984A1 - Detergent or cleaning agent with improved cleaning power

Info

Publication number: EP2958984A1
Application number: EP14702048.1A
Authority: EP
Inventors: Inga Kerstin Vockenroth; Nicole PLATH; Eva-Maria Wikker; Benoit Luneau
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2013-02-20
Filing date: 2014-02-03
Publication date: 2015-12-30
Also published as: WO2014127975A1; DE102013202772A1

Abstract

The invention relates to a detergent or cleaning agent with an improved cleaning power, in particular against enzyme-sensitive soiling, containing an enzyme, in particular a hydrolytic enzyme, and an itaconic acid polymer or salt thereof.

Description

"Detergents or cleaning agents with improved cleaning performance"

The present application is directed to a washing or cleaning agent containing an enzyme, in particular a hydrolytic enzyme, with improved cleaning performance, as well as methods for improving the cleaning performance of a detergent or cleaning agent.

The use of enzymes in detergents or cleaners is well established in the art. They serve to extend the range of services of the funds concerned according to their specific activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three hydrolyze proteins, starches and fats and thus contribute directly to soil removal. Cellulases are used in particular because of their tissue effect. Another group of washing or

Detergent enzymes are oxidative enzymes, in particular oxidases, which may be present in the

Interaction with other components preferably serves to bleach stains or to produce the bleaching agents in situ. In addition to these enzymes, which are subjected to constant optimization, further enzymes are constantly being made available for use in detergents or cleaning agents in order to be able to optimally address particular soiling, such as pectinases, β-glucanases, mannanases or other hemicellulases for the hydrolysis, in particular more specifically vegetable polymers.

Surprisingly, it was found that the addition of certain substances the

Cleaning performance of detergents or cleaners containing enzymes, especially hydrolytic enzymes, significantly improved.

The present invention is therefore based on the object to improve the cleaning performance (washing power) of detergents or cleaners, especially with regard to soiling, which are sensitive to degradation by enzymes, in particular by hydrolytic enzymes. A further object of the invention is to improve the cleaning performance of enzymes, in particular hydrolytic enzymes, in detergents or cleaners and the wash liquor formed by the washing or cleaning agents, in particular with regard to

Soiling that is sensitive to degradation by enzymes, in particular by

hydrolytic enzymes.

It has now been found that the addition of itaconic acid polymers and / or their salts to enzyme-containing detergents or cleaning agents can significantly improve the cleaning performance of these detergents or cleaners, in particular the cleaning performance of enzyme-sensitive soiling. In a first aspect, the present invention is therefore directed to a washing or cleaning agent, in particular a liquid washing or cleaning agent containing at least one enzyme, in particular at least one hydrolytic enzyme, preferably a protease, amylase, cellulase, hemicellulase, mannanase, tannase, Xylanase, xanthanase, β-glucosidase, carrageenase or lipase, more preferably comprising a protease, and further containing at least one itaconic acid polymer or salt thereof. The polyitaconate interacts synergistically with the enzyme when the agent is used

Cleaning performance.

Another object of the invention is a washing or cleaning process comprising the process steps

(a) providing a washing or cleaning solution comprising a washing or cleaning solution

Detergent containing (i) at least one enzyme, in particular a hydrolytic enzyme, preferably a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, β-glucosidase, carrageenase or a lipase, more preferably a protease, and ( ii) at least one itaconic acid polymer or salt thereof; and

(b) contacting a textile or a hard surface with the washing or cleaning solution according to (a).

Furthermore, the use of at least one Itaconsäurepolymers and / or salt thereof for improving the cleaning performance, in particular the cleaning performance of enzyme-sensitive soils, a detergent or cleaning agent, the at least one enzyme, in particular at least one hydrolytic enzyme, preferably a protease, amylase, cellulase , Hemicellulase, mannanase, tannase, xylanase, xanthanase, β-glucosidase, carrageenase or lipase, particularly preferably a protease, the subject of the present invention.

According to the invention it was found that the cleaning performance of washing or

Detergents, in particular with regard to their enzymatic cleaning performance, significantly improved when these agents at least one enzyme, preferably a hydrolytic enzyme, with at least one Itaconsäurepolymer or salt thereof is combined.

In the context of the invention, cleaning performance is understood to mean the removal of one or more soiling, in particular laundry soiling, which are sensitive to degradation by the particular enzyme, in particular for degradation by hydrolytic enzymes. Also included are also pale-sensitive laundry soiling. The distance can be measured by a brightening of the soiling detected as well as assessed visually. In the context of the invention, both the washing or cleaning agent, which comprises the enzyme and the washing or cleaning liquor formed by this agent, and the enzyme itself have a respective cleaning performance. The cleaning performance of the enzyme thus contributes to the cleaning performance of the agent and the washing or cleaning liquor formed by the agent.

The cleaning performance of detergents or cleaning agents based on the enzymatic activity used is improved by the addition of the itaconic acid polymer or salt thereof. Thus, the selected combination of enzyme, in particular hydrolytic enzyme, with an itaconic acid polymer or salt thereof is one way of achieving

Improve performance of detergents or cleaning agents in terms of their cleaning performance, in particular their enzyme-based cleaning performance.

The advantageousness of the combination of components (a) enzyme and (b) itaconic acid polymer or salt thereof is present when the agent is used, i. in the washing or cleaning fleet. A washing or cleaning liquor is understood to mean the use solution containing the washing or cleaning agent which acts on textiles or fabrics (wash liquor) or hard surfaces (cleaning liquor) and thus comes into contact with stains present on textiles or fabrics or hard surfaces. Usually, the washing or cleaning liquor arises when the washing or cleaning process begins and the washing or cleaning agent is dissolved, for example in a washing machine or in another suitable container in water or diluted with water.

The compositions described herein comprise at least one enzyme, but may also include multiple enzymes. In principle, all the enzymes established in the prior art for this purpose can be used in this regard. Preferably, it is one or more enzymes which can develop a catalytic activity in a washing or cleaning agent, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, xylanase, xanthanase, .beta.-glucosidase, Carrageenase, perhydrolase, oxidase, oxidoreductase and mixtures thereof. Preferred hydrolytic enzymes in the sense of component (a) include in particular proteases, amylases, in particular α-amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, β-glucanases, and mixtures thereof. Proteases, amylases and / or lipases and mixtures thereof are particularly preferred, and proteases are particularly preferred. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase®, and Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP® protease variants derived. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from the company Genencor, which was sold under the

Trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, sold under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P® by Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and their further developments improved for use in detergents or cleaners. The B. licheniformis enzyme is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar®ST. Further development products of this α-amylase are available from Novozymes under the trade name Duramyl® and Termamy Dultra, from Genencor under the name Purasta DOxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. B. amyloliquefaciens α-amylase is sold by Novozymes under the name BAN®, and variants derived from B. stearothermophilus α-amylase under the names BSG® and Novamyl®, also from Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the a-amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are suitable. Further advantageously usable commercial products are, for example, the amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter likewise of the

Company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Examples of lipases or cutinases which can be used according to the invention, which are contained in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors, are the lipases which are originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold for example by the company Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®.

Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases which are likewise useful are sold by Amano under the names Lipase CE®, Lipase P®, Lipase B® or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®. By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the preparations M1 Lipase.RTM. And Lipomax.RTM. Originally sold by Gist-Brocades and the enzymes marketed by Meito Sangyo KK, Japan, under the name Lipase MY-30®, Lipase OF® and Lipase PL® to mention also the product Lumafast® from the company Genencor.

Depending on the purpose, cellulases may be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement each other in terms of their various performance aspects. These performance aspects include in particular the contributions of the cellulase to the primary washing performance of the composition (cleaning performance), to the secondary washing performance of the composition (anti-redeposition effect or graying inhibition), to softening (tissue effect) or to the exercise of a "stone-washed" effect.A useful fungal, endoglucanase (EC ) -rich cellulase preparation, or their

Further developments are offered by the company Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, which are also available from Novozymes, are based on the 50 kD EG or the 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft®, Renozyme® and Celluclean®. Also usable are, for example, the 20 kD-EG from Melanocarpus available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®. Further commercial products of AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax® is available.

Further commercial products of Genencor are "Genencor detergent cellulase L" and lndiAge®Neutra. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from melanocarpus, in particular melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom. Furthermore, in particular for the removal of certain problem soiling, further enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases,

Pullulanases, pectin-cleaving enzymes and β-glucanases. The β-glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes. Hemicellulases which are particularly preferred according to the invention are mannanases which are sold, for example, under the trade names Mannaway® by the company Novozymes or Purabrite® by the company Genencor. The pectin-destroying enzymes in the context of the present invention are also counted enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin methoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectin esterase, pectin-pectin hydrolase, pectin-polymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin-polygalacturonase, Endo-polygalacturonase, poly-a-1, 4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1, 4-a-galacturonidase, exopolygalacturonase, poly (galacturonate) hydrolase, exo-D-galacturonase, exo-D Galacturonanase, exopoly-D-galacturonase, exo-poly-o galacturonosidase, exopolygalacturonosidase or exopolygalacturanosidase. Examples of enzymes suitable for this purpose are, for example, under the name Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes, and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.

Of all these enzymes, particular preference is given to those which have been stabilized per se with respect to oxidation in a comparatively stable manner or, for example, via point mutagenesis.

These include, in particular, the already mentioned commercial products Everlase® and Purafect® OxP as examples of such proteases and Duramyl® as an example of such an α-amylase.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases (which react at low H ₂ O ₂ concentrations as peroxidase), peroxidases, such as halo-, chloro-, bromo-, lignin, can also be used in the detergents or cleaners. , Glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases,

Polyphenol oxidases). Suitable commercial products are Denilite® 1 and 2 from Novozymes.

The enzymes to be used according to the invention can also be formulated together with accompanying substances, for example from the fermentation, or with stabilizers. The agents preferably contain enzymes in total amounts of 1 × 10 ^-8 to 5 weight percent based on active protein. Preferably, the enzymes are from 0.001 to 3 wt%, more preferably from 0.01 to 1.5 wt%, even more preferably from 0.05 to 1.25 wt%, and most preferably from 0.5 to 1, 0 wt .-% in these agents, wherein each enzyme contained can be present in the stated amounts. In liquid formulations, the enzymes are preferably used as enzyme liquid formulation (s).

The enzyme, in particular the hydrolytic enzyme, of which at least one is present in a washing or cleaning agent (namely as component (a)), supports the

Cleaning performance of the agent with regard to certain stains or stains. Particularly preferably, an agent according to the invention contains a plurality of enzymes, it being possible for the enzymes to belong to the same or different enzyme classes. Most preferably, the enzymes exhibit synergistic effects on their action against certain soils or stains, i. the enzymes contained in the middle composition mutually support each other in their cleaning performance.

Synergistic effects can not only exist between different enzymes, but in particular also occur between one or more enzymes and other ingredients of the agent used in a washing or cleaning process. Preferred for this purpose is an enzyme, in particular a hydrolytic enzyme, particularly preferably a protease, combined with at least one substance which interacts with the enzyme

Application of the agent causes a synergistic cleaning performance and which is a polyitaconate.

The polyitaconates used according to the invention are homo- or

Copolymers of itaconic acid (methylenesuccinic acid) and / or salts thereof. Examples of a particularly preferred substance to use is Itaconix® (polyitaconate sodium salt, Itaconix Corporation, Stratham, USA). The polyitaconates used are preferably homopolymers of itaconic acid and / or salts thereof, in particular their alkali metal salts, particularly preferably their sodium salts, preferably having an average molecular weight in the range from 1000 to 10,000 g / mol, preferably 2000-6000 g / mol, particularly preferably 2500 3500 g / mol. The term "polyitaconate" as used herein covers both itaconic acid polymers, i.e., polymers with free acid groups, as well as their salts.

The polyitaconate is preferably added to the washing or cleaning agent as a separate individual substance, ie not as a constituent of a further constituent of the washing or cleaning agent. Preferably, the polyitaconate is therefore free in the washing or cleaning agent, ie it is distributed in this and distributed as homogeneously as possible. In the case of liquid or gel detergents or cleaning agents, the polyitaconate is preferably dissolved or dispersed in them. Most preferably, the washing or cleaning agent does not contain the polyitaconate Part of the dosage form of the enzyme, in particular not as part of a

Enzyme granules.

Preferably, the agent is liquid or gel.

Advantageous cleaning performance is further provided by the fact that the polyitaconate is present in a certain concentration in the washing or cleaning agent. In a further embodiment of the invention, the means is therefore characterized in that the

Polyitaconate in a concentration of 0.1 to 5 wt .-%, in particular from 0.5 to 3 wt .-% is contained in the agent.

The compositions can be detergents for textiles, carpets or natural fibers, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, abrasives, glass cleaners, WC Be a freshener, etc. To the washing or

Detergents within the scope of the invention also include washing aids which are metered into the actual detergent during manual or automatic textile washing in order to achieve a further effect. Furthermore, detergents and cleaning agents in the context of the invention also include textile pretreatment and post-treatment agents, ie those agents with which the

Laundry item is brought into contact before the actual laundry, for example, to dissolve stubborn dirt, and also such agents that give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge in one of the actual textile laundry. Among the latter, i.a. calculated the fabric softener.

The washing or cleaning agents, as powdered solids, in recompressed

Particle form, as homogeneous solutions or suspensions may be present, in addition to the polyitaconates in principle all known and customary in such agents ingredients, wherein preferably at least one further ingredient is present in the agent.

For the development of the washing performance, the washing or cleaning agents used according to the invention preferably comprise (a) surfactant (s), particularly preferably a mixture of several surfactants from different substance classes. The first surfactant used according to the invention is preferably at least one anionic surfactant.

Suitable anionic surfactants in the washing or cleaning agents are all anionic surface-active substances. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, in the molecule glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups be included. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group.

Preferred anionic surfactants in the detergents or cleaners are alkyl sulfates,

Alkylpolyglykolethersulfate and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Preferred washing or cleaning agents used according to the invention comprise at least one surfactant of the formula

R -O- (AO) _n -SO ₃ ^" X ⁺ .

In this formula, R is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of carbon atoms are preferred. Particularly preferred radicals R are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₀ -C ₂ o-oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na ⁺ or K ⁺ including Na, with Na ^{+ being} extremely preferred. Additional cations X + can be selected from NH ₄ ⁺ , Mn ²⁺ , and mixtures thereof.

In summary, particularly preferred detergents or cleaners contain at least one anionic surfactant selected from fatty alcohol ether sulfates of the formula A-1

with k = 1 1 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-Ci ₂ -14 fatty alcohol ether sulfates with 2 EO (k = 1 1-13, n = 2 in formula A-1).

Further preferred detergents or cleaners additionally or alternatively contain at least one surfactant of the formula

R ³ -A-SO ₃ ^" Y ⁺ . In this formula, R ^{3 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the grouping -A- for -O- or a chemical bond. In other words, sulfate (A = O) or sulfonate (A = chemical bond) surfactants can be described by the above formula. Depending on the choice of the group A, certain radicals R ^{3 are} preferred. In the sulfate surfactants (A = O), R ^{3 is} preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms are preferred. Particularly preferred radicals R are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₀ -C ₂ o-oxo alcohols. Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na ⁺ or K ⁺ being preferred, Na ^{+ being} extremely preferred. Other cations Y + may be selected from NH ₄ ⁺ , / ₂ Zn ²⁺ , / ₂ Mg ²⁺ , / ₂ Ca ²⁺ , / ₂ Mn ²⁺ , and mixtures thereof.

Such particularly preferred surfactants are selected from fatty alcohol sulfates of the formula A-2

with k = 1 1 to 19. Very particularly preferred representatives are Na-Ci ₂ -14 fatty alcohol sulfates (k = 1 1-13 in formula A-2).

In the case of the sulfonate surfactants (A = chemical bond), which are preferred over the sulfate surfactants, R ^{3 is} preferably a linear or branched unsubstituted alkylaryl radical. Here, too, X is a monovalent cation or the nth part of an n-valent cation, the alkali metal ions being preferred, and Na ⁺ or K ⁺ being preferred, Na ^{+ being} extremely preferred. Additional cations X + can be selected from NH ₄ ⁺ ,

Mn ²⁺ , and mixtures thereof.

Such highly preferred surfactants are selected from linear or branched

Alkylbenzenesulfonates of the formula A-3

in which R ^' and R ^" together contain from 9 to 19, preferably from 1 to 15, and in particular from 1 to 13, carbon atoms A particularly preferred representative can be described by the formula A-3a:

In addition to the anionic surfactant (s), the detergents or cleaning agents used according to the invention may contain nonionic surfactant (s).

With particular preference, the washing or cleaning agent contains at least one nonionic surfactant from the group of fatty alcohol ethoxylates, since these surfactants also at low

Washing temperatures provide high performance detergents and cleaners and have excellent cold stability in the case of liquid preparations.

Accordingly, preferred detergents or cleaners additionally contain at least one nonionic surfactant of the formula

R ² -O- (AO) _m -H,

in the

R ^{2 is} a linear or branched, substituted or unsubstituted alkyl,

Aryl or alkylaryl radical,

AO for an ethylene oxide (EO) or propylene oxide (PO) grouping,

m stands for integers from 1 to 50.

In the abovementioned formula, R ^{2 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear,

unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ² are derived from Ci2-Ci ₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of C ₁₀ -C ₂ o-oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The subscript m is an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, m is the numbers 2, 3, 4, 5, 6, 7 or 8.

In summary, particularly preferred surfactants are selected from fatty alcohol ethoxylates of the formula C-1 with k = 1 1 to 19, m = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are C12-18 fatty alcohols with 7 EO (k = 1 1-17, m = 7 in formula C) -1 ).

Summarizing the above statements, washing or cleaning agents are preferred which

i) at least one anionic surfactant of the formula R -O- (AO) _n -SO ₃ ^" X ⁺ , ii) at least one anionic surfactant of the formula R ³ -A-SO ₃ ^" Y ⁺

iii) at least one nonionic surfactant of the formula R ² -O- (AO) _m -H,

contain, in which

R, R ² , R ³ independently of one another represent a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical,

AO for an ethylene oxide (EO) or propylene oxide (PO) grouping,

n, m for integers from 1 to 50,

A is -O- or a chemical bond,

X, Y independently of one another represent a monovalent cation or the nth part of an n-valent cation.

The surfactants i) and ii) have been described above as preferred surfactants a) of the formulas (A-2) and (A-3), the surfactant iii) as the preferred surfactant having the formula (C-1).

Preferred detergents or cleaners contain 2 to 25 wt .-%, preferably 2.5 to 20 wt .-%, more preferably 3 to 17.5 wt .-% and in particular 5 to 12.5 based on the total amount of the detergent or cleaning agent % By weight of fatty alcohol ether sulfate (e).

Further preferred washing or cleaning agents contain, based on the total amount of the washing or cleaning agent, 2.5 to 20 wt .-%, preferably 3 to 18 wt .-%, more preferably 3.5 to 17 wt .-%, even more preferably 4 to 15 wt .-% and in particular 5 to 10 wt .-% of surfactants from the group comprising C ₉ .i ₃ -Alkylbenzolsulfonate, olefinsulfonates, C 12-18 alkanesulfonates ester sulfonates, alk (en) ylsulfate, and mixtures thereof.

Further preferred detergents or cleaning agents contain 1 to 15% by weight, preferably 2 to 14% by weight, more preferably 2.5 to 13% by weight, even more preferably 3 to 15, based on the total amount of the detergent or cleaning agent 10 wt .-% and in particular 3.5 to 6 wt .-% fatty alcohol ethoxylate (s). Particularly preferred detergents or cleaners contain nonionic surfactants in specific amounts. Extremely preferred detergents or cleaners according to the invention are characterized in that the total amount of nonionic surfactants, based on the weight of the washing or cleaning agent, is 1 to 20% by weight, preferably 2 to 15% by weight, more preferably 2.5 to 12 , 5 wt .-%, even more preferably 3 to 1 1 wt .-% and in particular 4 to 10 wt .-% is.

It has proved to be advantageous for the cold washing performance when the washing or

Detergents also contain soap (s). Preferred washing or cleaning agents are characterized in that they contain, based on their weight, from 0.25 to 15% by weight, preferably from 0.5 to 12.5% by weight, more preferably from 1 to 10% by weight. , even more preferably 1, 5 to 7.5 wt .-% and in particular 2 to 6 wt .-% soap (s) included.

In addition, the washing or cleaning agent may contain other ingredients that further improve the performance and / or aesthetic properties of the detergent or cleaning agent. In the context of the present invention contains the washing or

Cleaning agent preferably additionally one or more substances from the group of

Builders, bleaches, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils,

Anti redeposition agents, grayness inhibitors, inlet preventer, anti-crease agents,

Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.

As builders that may be included in the washing or cleaning agent, are

in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Organic builders which may be present in the washing or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol are preferably used in liquid detergents or cleaners.

Preferred detergents or cleaners are liquid and preferably contain water as the main solvent. It is preferred that the washing or cleaning agent more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent or cleaning agent, water contains. Particularly preferred liquid detergents or cleaners according to the invention contain, based on their weight, 5 to 90% by weight, preferably 10 to 85% by weight, particularly preferably 25 to 75% by weight and in particular 35 to 65% by weight. Water. Alternatively, the detergents or cleaners can be water-free to water-free detergents or cleaners, the water content in a preferred embodiment being less than 10% by weight and more preferably less than 8% by weight, based in each case on the entire liquid detergent or cleaning agent is.

In addition, nonaqueous solvents can be added to the washing or cleaning agent. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range. Preferably, the solvents are 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 thereof

Solvent. However, it is preferred that the washing or cleaning agent contains an alcohol, in particular ethanol and / or glycerol, in amounts between 0.5 and 5 wt .-%, based on the total washing or cleaning agent. Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent.

The same applies to methods for cleaning hard surfaces.

Since an enzyme naturally already has an enzymatic activity and this unfolds in media that otherwise have no cleaning power, such as in buffer media, such a method may also consist only in that in addition to the added

Polyitaconate as the only further component an enzyme is applied, preferably in a buffer solution or in water. This represents another embodiment of this

Invention subject matter.

As already described above, the invention also relates to the use of at least one polyitaconate for improving the cleaning performance of a washing or cleaning agent containing at least one enzyme, in particular at least one hydrolytic enzyme, preferably a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase , Xanthanase, β-glucosidase, carrageenase or a lipase, more preferably a protease.

All facts, objects and embodiments described for the washing or cleaning agents are also applicable to the washing or cleaning process and the use and vice versa.

The liquid detergents or cleaners described herein, in particular the described low-water to water-free detergents or cleaners, can be filled into a water-soluble casing and thus be part of a water-soluble packaging. If the liquid washing or cleaning agent is packaged in a water-soluble casing, it is preferred that the content of water is less than 10 wt .-%, based on the total liquid detergent or cleaning agent, and that anionic surfactants, if present, in Form of their ammonium salts are present.

The neutralization with amines, unlike bases such as NaOH or KOH, does not lead to the formation of water. Thus, low-water liquid detergents or cleaners can be prepared which are directly suitable for use in water-soluble coatings.

A water-soluble packaging contains, in addition to the liquid washing or cleaning agent, a water-soluble coating. The water-soluble coating is preferably by a

formed water-soluble film material.

Such water-soluble packages can be obtained either by vertical methods

Formfüllversiegelns (VFFS) or thermoforming method can be produced. The thermoforming process generally includes forming a first layer of water-soluble film material to form protuberances for receiving one

Composition therein, filling the composition in the bulges, covering the bulges filled with the composition with a second layer of a water-soluble film material and sealing the first and second layers together at least around the bulges.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrap may consist of one or two or more layers of the water-soluble

Foil material are formed. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.

The water-soluble package comprising the liquid detergent or water-soluble wrapper may have one or more chambers. The liquid detergent may be contained in one or more chambers, if any, of the water-soluble coating. The amount of liquid detergent or cleaning agent preferably corresponds to the full or half dose needed for a wash.

It is preferred that the water-soluble coating be polyvinyl alcohol or a

Contains polyvinyl alcohol copolymer.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose

Molecular weight in the range of 10,000 to 1,000,000 gmol ^"1 , preferably from 20,000 to 500,000 gmol ^{" 1} , more preferably from 30,000 to 100,000 gmol ^"1 and in particular from 40,000 to 80,000 gmol ^{" 1} .

A suitable for preparing the water-soluble coating sheet material may additionally polymers, selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and

Mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof. Suitable water-soluble films for use in the casings of the water-soluble

Packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The water-soluble packages may have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.

The water soluble package may include one or more chambers for storing one or more agents. If the water-soluble packaging has two or more chambers, at least one chamber contains the liquid washing or cleaning agent. The other chambers may each contain a solid or a liquid washing or cleaning agent.

Examples

Example 1: Calcium Binding Capacity

The calcium binding capacity of the polyitaconates used was tested by adding 5 mL of a solution (1 g / mL) of the polyitaconate Itaconix® (Itaconix Corporation, Stratham, USA) to 250 mL of water at pH 8.5 and 30 ° dH at 25 ° C and the pH was readjusted to 8.5, if necessary. Then, after 5 minutes using a calcium-sensitive electrode, the residual hardness of the solutions was determined. For comparison, the residual hardnesses of Acusol 445N (polycarboxylate, Na salt, Rohm & Haas / Dow Chemical) and Dequest® P9000 (poly (maleic acid), Thermphos) were determined under identical conditions.

Table 1 :

The results show that the calcium binding capacity of the polyitaconate is significantly better than that of the polycarboxylate and the poly (maleic acid).

Example 2: Improvement of the cleaning performance

Table 2: Composition liquid detergent

All data in% by weight For the washing tests were household washing machines (Miele W1514) with 3.5 kg

Accompanied underwear and the soiled cloth rag loaded. In addition, 70 g / 66 ml of the detergent to be tested were metered in and washed at 40.degree. Detergent A from Table 2 was used as a reference and compared with detergent B according to the invention, which contained 1.5% of the polyitaconate, and with another reference detergent C which contained 1.5% polyacrylate. After hanging drying and mangling of the cloth rags their whiteness was determined spectrophotometrically (Minolta CR400-1).

The results are given in Table 3 and are averages of 6 determinations. The soiled textiles were bought.

Indicated are the differences of the remission values to the standard detergent in the 6-fold determination. The addition of the polyitaconate leads to an improvement in the washability of various stains, in particular of enzyme-sensitive stains. The addition of the polyitaconate in a detergent or cleaner results in a greater improvement in stain removal than when the same amount of a polyacrylate is added.

Table 3: Cleaning performance on various stains

It can be clearly seen from the table that the use of polyitaconates as defined herein leads to a significant improvement in cleaning performance. It is the

Improvement in the use of polyitaconates better than in the case of using polyacrylates. The latter show only tendential improvements that are smaller than in the case of polyitaconate.

Claims

claims

1. washing or cleaning agent containing at least one enzyme, in particular

at least one hydrolytic enzyme, preferably a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, β-glucosidase,

Carrageenase or lipase, particularly preferably a protease, characterized in that the washing or cleaning agent further contains at least one Itaconsäurepolymer or salt thereof.

2. washing or cleaning process comprising the process steps

(a) providing a washing or cleaning solution comprising a washing or cleaning agent which contains (i) at least one enzyme, in particular a hydrolytic enzyme, preferably a protease, amylase, cellulase,

Hemicellulase, mannanase, tannase, xylanase, xanthanase, β-glucosidase, carrageenase or a lipase, more preferably a protease, and (ii) at least one itaconic acid polymer or salt thereof; and

3. The embodiment according to any one of claims 1 or 2, characterized in that the itaconic acid polymer or salt thereof is a homopolymer of itaconic acid or a salt thereof, in particular an alkali metal salt, preferably a sodium salt thereof.

4. The embodiment according to any one of claims 1 to 3, characterized in that the itaconic acid polymer or salt thereof has an average molecular weight in the range of 1000 to 10,000 g / mol, preferably 2000-6000 g / mol, particularly preferably 2500-3500 g / mol ,

5. The embodiment according to any one of claims 1 to 4, characterized in that the itaconic acid polymer or salt thereof in the washing or cleaning agent in an amount of 0.1 to 5 wt .-%, preferably 0.5-3 wt.% Based is contained on the total weight of the washing or cleaning agent.

6. Embodiment according to one of claims 1 to 5, characterized in that the at least one enzyme in the washing or cleaning agent in an amount of 1 x 10 ^{~ 8} to 5 wt .-% percent based on active protein, in particular 0.001 to 3 Wt .-%, preferably from 0.01 to 1, 5 wt .-%, more preferably from 0.05 to 1, 25 wt .-% and particularly preferably from 0.5 to 1, 0 wt .-% based on the total weight of the washing or cleaning agent is included.

7. Embodiment according to one of claims 1 to 6, characterized in that the washing or cleaning agent further comprises at least one further component, preferably at least two further constituents selected from the group consisting of

Surfactants, preferably a mixture of several different surfactants, more preferably a mixture of at least one anionic and at least one nonionic surfactant, builders, bleaching agents, electrolytes, non-aqueous

Solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents,

Grayness inhibitors, inlet preventer, anti-crease agents,

Contains color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.

8. The embodiment according to any one of claims 1 to 7, characterized in that the washing or cleaning agent is present in liquid form in a water-soluble sheath, in particular a water-soluble sheath of a water-soluble film material, wherein the water-soluble film material preferably contains polyvinyl alcohol or a polyvinyl alcohol copolymer.

9. Use of at least one Itaconsäurepolymer or salt thereof to improve the cleaning performance, in particular the cleaning performance of enzyme-sensitive

Stains, a washing or cleaning agent comprising at least one enzyme, in particular at least one hydrolytic enzyme, preferably a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, ß-glucosidase, carrageenase or lipase, particularly preferably a protease ,