EP3472289A1

EP3472289A1 - Concentrated liquid detergents containing polymers

Info

Publication number: EP3472289A1
Application number: EP17731520.7A
Authority: EP
Inventors: Ulrich Pegelow; Sabine SCHÜMANN; Simon PLUSZYNSKI; Anna KLEMMER; Thorsten Bastigkeit
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2016-06-16
Filing date: 2017-06-14
Publication date: 2019-04-24
Anticipated expiration: 2037-06-14
Also published as: WO2017216215A1; EP3472289B1; US20190112548A1; DE102016210743A1

Abstract

The invention relates to highly concentrated liquid detergents with a surfactant content of 30 wt.% and more, also containing polymers in concentrations of 2 wt. % or more, and displaying optimised product stability, said detergent having a specifically adapted surfactant system containing alkyl ether alkoxylates, alkyl(poly)gylcosides and additional surfactants. The invention also relates to methods for washing textiles using the described detergents and to the use thereof.

Description

"Concentrated liquid detergents containing polymers"

The present application is directed to highly concentrated liquid detergents having surfactant contents of 30% by weight and more, which simultaneously contain polymers in concentrations of 2% by weight or more and exhibit optimized product stability by having a specially adapted surfactant system. Also included are processes for washing textiles using the detergents described and their use.

Liquid detergents are known in the art and have become increasingly popular with consumers in recent years as they offer a number of advantages over solid detergents. These include, among other things, the simpler dosage, addition and dissolution in the wash liquor. In addition, they are perceived as safer and less aggressive to the textiles and the environment. Especially for the washing of colored textiles, they have gained more and more popularity since their market launch.

There is a general trend in the market towards more highly concentrated liquid detergents, since these are associated with lower use of resources, which is in particular due to a lower transport weight and reduced bottle size. In addition, such highly concentrated agents are preferred by consumers because they require small storage space in the households.

Although such agents are advantageous in terms of handling and consumer acceptance, the known agents suffer from disadvantages in terms of their stability, especially with longer storage times. These disadvantages are further compounded by the trend towards higher concentrated products. For highly concentrated liquid detergents, the challenge is to accommodate more of the required top performers (including surfactants, polymers, enzymes, chelants, perfume, optical brightener) in a smaller volume of liquid.

In order to achieve a good washing performance from the consumer's point of view, polymeric ingredients are increasingly used in modern liquid detergents. Often these are essentially nonionic or anionic polymers of different functionality. Important groups are so-called soil release polymers, dye transfer inhibitors (DTIs), anti-redeposition agents and polymeric dispersants. A particular challenge is to ensure a stable formulation of the polymers, since the compatibility of the polymeric ingredients of a liquid formulation decreases with increasing surfactant concentration. As a result, cloudiness occurs, Sedimentation or phase separations on. These not only affect the aesthetic appearance of the recipe but also adversely affect the washing performance.

There is therefore a need for improved highly concentrated liquid detergent formulations which have improved properties in view of the problems mentioned, i. in particular, allow to stably formulate larger quantities of polymeric constituents.

It has now surprisingly been found that the above-mentioned disadvantages of highly concentrated liquid detergents, i. which allows detergents with surfactant contents of 30% by weight or more to be overcome by using a specific surfactant combination that allows stable formulation of polymeric ingredients in amounts of 2% by weight or more.

In a first aspect, therefore, the present invention relates to liquid detergents having a surfactant concentration of> 30% by weight, based on the total weight of the composition, preferably in the range of 30 to 45% by weight, more preferably 32 to 38% by weight, and a concentration of polymeric constituents of> 2% by weight, based on the total weight of the composition, preferably 2 to 10% by weight, more preferably 3 to 5% by weight, characterized in that the composition comprises a surfactant system which nonionic surfactants in an amount of 5 to 20 wt .-% based on the total weight of the composition, preferably 8 to 15 wt .-%, wherein the nonionic surfactants comprise at least one alkyl ether and at least one alkyl (poly) glycoside, wherein the weight ratio of alkyl ether to alkyl (poly) glycoside is 1: 2 to 5: 1, preferably 1: 1 to 3: 1.

In a further aspect, the present invention relates to the use of a liquid detergent according to the invention for washing textiles.

In a further aspect, the present invention relates to a process for the cleaning of textiles, characterized in that in at least one process step, a liquid detergent according to the invention is used.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are by weight unless otherwise specified, based on the total weight of the compositions / composition. Numeric ranges given in the format "from x to y" include the values mentioned If numeric ranges are specified in this format, it goes without saying that all ranges resulting from the combination of the various endpoints are also captured.

"At least one" as used herein refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more In the context of components of the compositions described herein, this indication does not refer to the absolute amount The term "at least one anionic surfactant" therefore means, for example, one or more different anionic surfactants, ie one or more different types of anionic surfactants. The amounts given, together with quantities, refer to the total amount of the corresponding type of ingredient.

"About", "approximately." or "approximately" as used herein in reference to a numerical value refers to the corresponding numerical value ± 10%, preferably ± 5%.

The detergents described herein may be detergents for textiles or natural fibers. Detergents in the context 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 or to enhance an effect. Furthermore, detergents within the scope of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the item of laundry is brought into contact before the actual washing, for example for dissolving stubborn soiling, and also agents which are in a downstream of the actual textile laundry step give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Among the latter, i.a. calculated the fabric softener. In preferred embodiments, however, it is a textile detergent.

In various embodiments of the invention, the liquid detergents have a total surfactant content of 30 to 45% by weight, preferably 32-38% by weight, of which 5-20% by weight, preferably 8 to 15% by weight, of nonionic surfactants and the remainder anionic, cationic, zwitterionic and / or amphoteric surfactants, but preferably anionic surfactants.

The nonionic surfactants comprise at least one alkyl ether. In a preferred embodiment of the invention, the nonionic surfactant agents described herein contain at least one fatty alcohol alkoxylate having the formula below

R -0- (AO) m H, wherein R is a linear or branched alkyl radical, AO is an ethylene oxide (EO) or propylene oxide (PO) moiety and m is an integer from 1 to 50. In the above formula, R represents a linear or branched, substituted or unsubstituted alkyl radical. In a preferred embodiment of the present invention, R is a linear or branched, preferably unsubstituted, alkyl radical having from 5 to 30 carbon atoms, preferably from 7 to 25 carbon atoms and especially from 10 to 19 carbon atoms. Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and mixtures thereof, with the even number of carbon atoms being preferred. Particularly preferred radicals R are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols having 10 to 19 carbon atoms.

AO is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index m is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7. The composition according to the invention can comprise mixtures of nonionic surfactants which have different degrees of ethoxylation.

In summary, particularly preferred fatty alcohol alkoxylates are those of the formula with k = 9 to 17, m = 3, 4, 5, 6, or 7. Very particularly preferred representatives are fatty alcohols having 10 to 18 carbon atoms and 7 EO (k = 1 1 to 17, m = 7).

Such fatty alcohol ethoxylates are available under the brand names 45-7 Dehydol LT7 ^® (Cognis), Lutensol ^® A07 (BASF) Lutensol ^® M7 (BASF), and Neodol ^® (Shell Chemicals).

Furthermore, the liquid detergent contains as nonionic surfactant at least one alkyl (poly) glycoside of the formula

R ² 0- [G] _P ,

R ^{2 represents} a linear or branched alkyl of 8 to 26, preferably 8 to 20, more preferably 8 to 18, 8 to 10 or 12 to 16 carbon atoms, G represents a sugar residue of 5 or 6 carbon atoms and p represents numbers of 1 until 10 stands. G can be for sugar with 5 (pentoses) or 6 (hexoses) carbon atoms, in particular glucose, the degree of oligomerization p can be from 1 to 10. Particularly preferred alkyl (poly) glycosides are derived from glucose and can be described by the formula:

in which n is 7 to 15, in particular 7 to 9 or 1 to 15, and p is a number from 1 to 10.

The degree of oligomerization p in the formulas given above is preferably <8, more preferably <6, even more preferably <4 and in particular <2. Particularly preferred surfactant mixtures or washing or cleaning agents according to the invention contain nonionic surfactants in which p is from 1 to 4 1, 8 stands.

These refracted degrees of oligomerization are realized by mixtures containing varying amounts of surfactants of the above formulas in which p represents the single molecule as an integer, preferably 1, 2, 3 or 4.

In summary, preferred detergents according to the invention are characterized in that they contain Ce-16, in particular Ce-io or Ci2-i6-alkyl-oligo (1, 4) -glucoside. Suitable alkyl (ply) glycosides are available, for example, under the trade names Plantacare® or Plantaren® from BASF (BASF SE, DE) and include, among others, Plantacare® 220 UP (APG 220 UP) and Plantaren® 1200 UP NP (APG 600 UP) ,

The agents of the invention contain the alkyl ethers, in particular the above-described fatty alcohol alkoxylates and alkyl polyglycosides in weight ratios of 1: 2 to 5: 1, preferably 1: 1 to 3: 1. In this case, the amount of alkyl ether / fatty alcohol alkoxylate, for example, 5 to 15 wt .-%, preferably 6 to 10 wt .-%, and / or the amount of alkyl (poly) glycoside, for example, 2 to 8 wt .-%, preferably 3 to 5 % By weight, in each case based on the total weight of the composition.

In various embodiments, the liquid detergent contains no other nonionic surfactants other than these two types of nonionic surfactants.

Alternatively, however, the detergent may contain other nonionic surfactants as long as the total content of nonionic surfactants in the agent does not exceed 20% by weight. As further nonionic surfactants, for example amine oxides can be contained. As amine oxide, in principle all amine oxides established for this purpose in the prior art are compounds which have the formula RR ² R ³ NO, wherein each R, R ² and R ³ independently of the others is an optionally substituted hydrocarbon chain having 1 to 30 carbon atoms , usable. Particularly preferred amine oxides are those wherein R is alkyl of 12 to 18 carbon atoms and R ² and R ^{3 are} each independently alkyl of 1 to 4 carbon atoms, especially alkyl dimethylamine oxides of 12 to 18 carbon atoms. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide or lauryldimethylamine oxide.

Other usable nonionic surfactants may be, for example

polyol

alkoxylated triglycerides,

alkoxylated fatty acid alkyl esters of the formula R ³ CO- (OCH ₂ CHR ⁴ ) wOR ⁵ ,

in the R ³ CO for a linear or branched, saturated and / or unsaturated acyl radical

6 to 22 carbon atoms, R ^{4 is} hydrogen or methyl and R ^{5 is} linear or branched

Alkyl radicals having 1 to 4 carbon atoms and w is 1 to 20,

hydroxy mixed,

Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters, addition products of ethylene oxide with fatty acid alkanolamides and fatty amines, and

Fatty acid N-alkyl glucamides.

The agents described herein may also contain several of the nonionic surfactants described above.

The residual content of surfactants is preferably made up by anionic surfactants. In various embodiments, therefore, the compositions do not contain any cationic surfactants and preferably also no amphoteric or zwitterionic surfactants.

Particularly suitable anionic surfactants are those of the sulfonate type and preferably alkylbenzenesulfonates, olefinsulfonates, ie. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from monoolefins having 12 to 18 carbon atoms with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation into consideration. Also suitable are alkanesulfonates having 12 to 18 carbon atoms and the esters of Sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula

in which R ^' and R ^"are independently hydrogen or alkyl and together contain from 9 to 19, preferably 9 to 15 and in particular 9 to 13 carbon atoms A particularly preferred representative is sodium dodecylbenzylsulfonate.

Alk (en) ylsulfates are the salts of the sulfuric acid half-esters of fatty alcohols containing 12 to 18 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the oxo alcohols having 10 to 20 carbon atoms and those half-esters of secondary alcohols these chain lengths are preferred. Of washing technology interest, the alkyl sulfates having 12 to 16 carbon atoms and alkyl sulfates having 12 to 15 carbon atoms and alkyl sulfates having 14 and 15 carbon atoms are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also particularly suitable are the secondary alkanesulfonates. "Secondary" as used herein refers to the well-known chemical meaning of this term, and indicates that the carbon atom to which the sulfonate group is covalently bonded continues to have two covalent bonds to two organic (alkyl) radicals, ie carbon atoms, and having a covalent bond to a hydrogen atom Together with the carbon atom to which they are attached, the two organic (alkylic) radicals form a linear or branched alkyl having 1 to 50 carbon atoms. in order to compensate the negative charge of the sulfonate group, alkanesulfonate the present invention further comprises any cation, preferably selected from the group Na ^+, K ^+, NH4 ^+, Α Zn ^2+, V Mg ^2+, Ca ²⁺ V, V Mn ²⁺ and mixtures thereof, more preferably Na ⁺ .

In various embodiments of the invention, secondary alkanesulfonate is one of the formula

R is CH (S0 ₃ X ⁺ ) R ² , each R and R ^{2 is} independently a linear or branched alkyl of 1 to 20 carbon atoms and form with the carbon atom to which they are attached a linear or branched alkyl, preferably of 10 to 30 carbon atoms, preferably of 10 to 20 carbon atoms and X ^{+ is} selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , / ₂ Zn ²⁺ , / ₂ Mg ²⁺ , / ₂ Ca ²⁺ , / ₂ Mn ²⁺ and mixtures thereof, preferably Na ⁺ . Particularly preferred are secondary alkanesulfonates of the formula

H3C- (CH2) n-CH (S03-X ⁺⁾ - _(CH2) m-CH3, wherein m and n are independently an integer between 0 and 15. Preferably, m and n are independently an integer of 7-15, and preferably between 1 1 and 14. X ⁺ is further selected from the group Na ^+, K ^+, NH ₄ ⁺ ^_1/2 Zn ²⁺ ^_1/2 mg ^2+, ^_1/2 Ca ^2+, ^_1/2 Mn ^2+, and mixtures thereof, preferably Na ^+.

Further suitable anionic surfactants are those of the sulfate type and in particular the alkyl ether sulfates.

Preferred alkyl ether sulfates are those of the following formula wherein R ^{4 is} a linear or branched alkyl having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms, and preferably having 10 to 19 carbon atoms. Further, AO in the above formula is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide (EO) group, and n is an integer of 1 to 50, preferably 1 to 20, and preferably of 2 to 10 is. X ⁺ is any cation and is preferably selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , Mn ² and mixtures thereof, more preferably Na ⁺ .

In the above formula, R ^{4 is} a linear or branched, substituted or unsubstituted alkyl radical. In a preferred embodiment of the present invention, R ^{4 is} a linear or branched, preferably unsubstituted, alkyl radical having from 5 to 30 carbon atoms, preferably from 7 to 25 carbon atoms and especially from 10 to 19 carbon atoms. Preferred radicals R ⁴ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and mixtures thereof, with the even number of carbon atoms being preferred. Particularly preferred radicals R ⁴ are derived from fatty alcohols having 12 to 19 carbon atoms, for example from Coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of oxo alcohols having from 10 to 19 carbon atoms.

The alkyl ether sulfate is preferably one of the formula where k = 1 1 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na fatty alcohol ether sulfates having 12 to 18 carbon atoms and 2 EO (k = 1 1 to 13, n = 2). The stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product. Generally, the degrees of alkoxylation indicated represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).

The surfactants described above are used in conventional amounts, the amount being selected so that the total surfactant content of the inventive compositions, as described above,> 30 wt .-%, usually up to 45 wt .-% is. Preferred amounts of surfactant are in the range of 32 to 38 wt .-%. In preferred embodiments, the agents contain at least one anionic, preferably at least two anionic surfactants and at least two nonionic surfactants, as defined above. The anionic surfactants are preferably alkylbenzenesulfonates, as described above, which are usually present in amounts of from 10 to 25% by weight, preferably from 12 to 20% by weight, particularly preferably from 14 to 18% by weight, in the compositions , Additionally or alternatively, the agents may also contain alkyl ether sulfates, usually in amounts of 2 to 10 wt .-%, in particular 3 to 8 wt .-%. The total content of anionic surfactants is typically 15 to 25% by weight. In addition to the anionic surfactants, nonionic surfactants are present in amounts of 5 to 20% by weight, preferably 8 to 15% by weight. The nonionic surfactants comprise at least one alkyl ether, preferably fatty alcohol alkoxylate, as described above, typically in amounts of from 5 to 15 wt.%, Preferably 6 to 10 wt.%, And at least one alkyl (poly) glycoside as described above typically in amounts of 2 to 8 wt .-%, preferably 3 to 5 wt .-%. In particularly preferred embodiments, the liquid detergents therefore contain 12-20, preferably 14-18 wt .-% alkylbenzenesulfonates, 2 to 10, preferably 3 to 8 wt .-% alkyl ether sulfates, 5-15, preferably 6-10 wt .-% alkyl ethers, in particular fatty alcohol alkoxylates, and 2-8, preferably 3 to 5 wt .-% alkyl (poly) glycosides.

Furthermore, the detergent may contain at least one fatty acid soap. These are particularly advantageous for the cold washing performance. Preferred detergents are therefore characterized in that they contain, based on their weight, from 0.1 to 15% by weight, preferably from 0.2 to 12.5% by weight, more preferably from 0.5 to 3% by weight, of soap (n) included. Particularly preferred are soaps of fatty acids having 12 to 18 carbon atoms. The fatty acid soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, they are in the form of their sodium salts and / or ammonium salts.

The liquid detergents described herein further contain 2% or more by weight, based on the total weight of the composition, preferably 2 to 10% by weight, more preferably 3 to 5% by weight of polymeric ingredients, especially soil release polymers or SRPs), anti-redeposition agents, color transfer inhibitors (DTIs), polymeric dispersants, and combinations of the foregoing.

In particular, oligoesters are obtainable as SRPs from preferably terephthalic acid, isophthalic acid, sulfoisophthalic acid and / or methyl esters thereof, aliphatic dicarboxylic acids (saturated and / or unsaturated), for example adipic acid, and / or their anhydrides, aliphatic substituted dicarboxylic acids, for example nonylsuccinic acid, alkylene glycols (ethylene, 1, 2-propylene, 1, 2-butylene glycol), polyethylene glycols, alkyl polyethylene glycols, Polyethylenglykolbenzoesäureester, Polyethylenglykolsulfobenzoesäureester and optionally alkanolamines used. Preference is given to polymers based on terephthalate PEG, as are commercially available, for example, under the trade name Texcare®. Alternatively (co) polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol can also be used.

Suitable soil release polymers are generally already well known in the art. In particular, therefore, all known in the art for this purpose polymers can be used.

In order to effectively suppress dye release and / or dye transfer to other fabrics during the washing and / or cleaning of dyed fabrics, the composition of the invention may contain a dye transfer inhibitor. It is preferred that the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. Suitable polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride and mixtures thereof. Particular preference is given to using polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as color transfer inhibitor.

Particularly suitable as anti-redeposition agents are polycarboxylates. Suitable materials can be prepared by the polymerization or copolymerization of unsaturated carboxylic acid monomers such as acrylic acid, maleic acid (or anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylmalonic acid. Particularly preferred are acrylate polymers and acrylic / maleic copolymers.

Suitable SRPs, anti-redeposition agents and DTIs are also described, for example, in International Patent Publication WO 2009/153184 A1 on pages 25-39 under the headings "dye tranfer inhibitors", "anti redeposition agents" and "soil release polymers." The disclosure of this document with respect to said polymers, is incorporated herein by reference in its entirety.

In various embodiments of the invention, the polymers contained in the agents comprise at least one SRP and optionally at least one DTI.

The liquid detergents described herein further preferably contain at least one enzyme. The at least one enzyme may be any enzyme known in the art capable of exhibiting catalytic activity in a detergent or cleaning agent, and includes but is not limited to, for example, proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin cleaving enzymes, tannases, xylanases, xanthanases, β-glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof. In a preferred embodiment, the at least one enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof. These enzymes are, in principle, of natural origin, but starting from the natural molecules, improved variants are available for use in detergents or cleaners, 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 Genencor, sold under the trade name Protoso D by Advanced Biochemicals Ltd. , Thane, India, under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and under the name Proteinase K-16 from Kao Corp. , Tokyo, Japan, available enzymes. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus.

Examples of amylases are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from ß. stearothermophilus and their improved for use in detergents or cleaners further developments. The enzyme from ß. licheniformis 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 Purastar®OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The α-amylase of β. amyloliquefaciens is marketed by the company Novozymes under the name BAN®, and derived variants of the α-amylase from β. stearothermophilus 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 cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the α-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 also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention.

Examples of useful lipases or cutinases, which are contained in particular because of their triglyceride-cleaving activities, but also 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, originally isolated from Fusarium solani pisi and Humicola insolens have been. 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 its further developments is offered by the company Novozymes under the trade name Celluzyme® The products Endolase® and Carezyme® likewise available from the company Novozymes are based on the 50 kD-EG or the 43 kD-EG H. insolens DSM 1800. Other commercially available products of this company are Cellusoft®, Renozyme® and Celluclean.RTM .. Also usable are, for example, the 20 kD-EG from Melanocarpus, those from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® Other commercial products of AB Enzymes are Econa se® 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-splitting 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, for example, among the Trade name Mannaway® from 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 as peroxidase at low H 2 O 2 concentrations), peroxidases, such as halo, chloro, bromo, lignin, glucose, can also be present in the detergents, in particular liquid detergents or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products are Denilite® 1 and 2 from Novozymes.

The liquid detergents contain the at least one enzyme in amounts established in the prior art. Thus, the at least one enzyme in a total amount of 1 x 10 ^{~ 8} to 5 wt .-% based on active protein or in a total amount of 0.001 to 3 wt .-%, or 0.01 to 1, 5 wt. % or 0.05 to 1, 25 wt .-% contained. The amounts given are to be understood so that any enzyme contained can be contained in the stated amounts. The enzymes are preferably used as enzyme liquid formulation (s).

The at least one enzyme present in a detergent or cleanser aids the cleaning performance of the agent on certain soils or stains. Particularly preferably, an agent according to the invention contains a plurality of enzymes, the enzymes being the same or different enzyme classes. Particularly preferably, the enzymes show synergistic effects with respect to their action against certain stains or stains, ie the enzymes contained in the composition mutually support each other in their cleaning performance.

In addition, the detergent may contain other ingredients that further improve the performance and / or aesthetic properties of the detergent. In the context of the present invention, the detergent preferably additionally contains one or more substances from the group of builders / complexing agents, bleaching agents, electrolytes, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, grayness inhibitors, anti-shrinkage agents, anti-crease agents, antimicrobial agents, germicides , Fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents, softening components, pH adjusters and UV absorbers.

As a bleaching agent can serve all substances that destroy or absorb dyes by oxidation, reduction or adsorption and thereby discolor materials. These include, among others, hypohalite-containing bleach, hydrogen peroxide, perborate, percarbonate, peroxoacetic acid, diperoxoazelaic acid, diperoxododecanedioic acid, and oxidative enzyme systems. However, liquid detergents are typically free of non-enzymatic bleaches.

Suitable builders which may be present in the detergent are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, phosphonates, organic di- and polycarboxylic acids or salts thereof and mixtures of these substances.

Organic builders which may be present in the detergent 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. Likewise suitable and preferred are aminocarboxylic acids, in particular glutamic diacetic acid (GLDA) and methylglycine diacetic acid (MGDA).

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.

In liquid detergents, preference is given to using soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol.

The detergents may additionally contain phosphonates, such as HEDP (1-hydroxyethane-1, 1-diphosphonic acid) or DTPMP (diethylene triamine penta (methylene phosphonate), as builders and complexing agents.

Preferred liquid detergents preferably contain water as the main solvent. It is preferred that the detergent more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent, water. Particularly preferred liquid detergents contain - based on their weight - 5 to 65 wt .-%, preferably 10 to 60 wt .-%, particularly preferably 25 to 55 wt .-% and in particular 30 to 50 wt .-% water. Alternatively, the liquid detergents may be low-water to water-free detergents, 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 total liquid detergent ,

In addition, nonaqueous solvents may be added to the detergent. 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. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexyleneglycol, 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-ol methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents. Particular preference is given to 1,2-propanediol and glycerol. It is preferred that the detergent contains such an alcohol, in particular 1, 2-propanediol and / or glycerol, in amounts of between 0.5 and 15 wt .-%, based on the total detergent.

The detergents described herein, in particular the described low-water to anhydrous liquid detergents, can be filled into a water-soluble casing and thus be part of a water-soluble packaging. If the detergent is packaged in a water-soluble casing, it is preferred that the content of water is less than 10% by weight, based on the total detergent.

A water-soluble packaging contains, in addition to the detergent, a water-soluble coating. The water-soluble coating is preferably formed by a water-soluble film material.

Such water soluble packages can be made by either vertical fill seal (VFFS) or thermoforming methods.

The thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers 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 wrapper may be formed of one or two or more layers of the water-soluble film material. 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 detergent and the 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 preferably corresponds to the full or half dose needed for a wash.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a 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 is in the range of 10,000 to 1,000,000 g / mol, preferably 20,000 to 500,000 g / mol, more preferably 30,000 to 100,000 g / mol and especially from 40,000 to 80,000 g / mol.

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 sold by the company 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 a liquid detergent. The other chambers may each contain a solid or a liquid detergent.

Another object of the invention is a process for the cleaning of textiles, which is characterized in that in at least one process step, an inventive agent and the use of a liquid detergent according to the invention for washing textiles.

These include both manual and mechanical processes, with mechanical processes being preferred. Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned and washed off after the contact time, or that the items to be cleaned are otherwise treated with a detergent or a solution or dilution of this product. All conceivable washing methods can be enriched in at least one of the method steps to the application of a detergent according to the invention and then represent embodiments of the present invention. All facts, objects and embodiments described for means according to the invention are also applicable to this subject of the invention. Therefore, reference is made at this point expressly to the disclosure in the appropriate place with the statement that this disclosure also applies to the above inventive methods and uses.

Examples

Table 1: Detergent formulation, components in% by weight

The formulation was stable after 12 weeks of storage at room temperature. A comparison formulation containing only nonionic surfactant only fatty alcohol 7EO showed phase separation already after 2 weeks.

Claims

Patent claims

1. Liquid detergent with a surfactant concentration of >30% by weight based on the total weight of the agent, preferably in the range from 30 to 45% by weight, more preferably 32 to 38% by weight, and a concentration of polymeric components of > 2% by weight based on the total weight of the agent, preferably 2 to 10% by weight, more preferably 3-5% by weight, characterized in that the agent contains a surfactant system which contains non-ionic surfactants in an amount of 5 to 20% by weight based on the total weight of the agent, preferably 8 to 15% by weight, the nonionic surfactants comprising at least one alkyl ether and at least one alkyl (poly) glycoside, the weight ratio of alkyl ether to alkyl (poly) glycoside 1:2 to 5:1, preferably 1:1 to 3:1.

2. Liquid detergent according to claim 1, characterized in that the agent comprises 5-20% by weight, preferably 8 to 15% by weight, of nonionic surfactants and the remainder are anionic, cationic, zwitterionic and/or amphoteric surfactants, preferably anionic surfactants .

3. Liquid detergent according to claim 1 or 2, characterized in that

(1) the at least one alkyl ether is a fatty alcohol alkoxylate, preferably a C10-18 fatty alcohol ethoxylate with 3-7EO, more preferably a C10-18 fatty alcohol ethoxylate with 7EO;

(2) the at least one alkyl (poly) glycoside is a compound of the formula

R ² 0-[G] _P is,

in which R ² is a linear or branched alkyl with 8 to 26, preferably 8 to 20, more preferably e to 18, in particular 8 to 10 or 12 to 16 carbon atoms, G is a sugar residue with 5 or 6 carbon atoms, in particular glucose, and p represents numbers from 1 to 10, preferably <8, <6, <4 or <2, most preferably 1.4 to 1.8

4. Liquid detergent according to one of claims 1 to 3, characterized in that the agent contains, based on the total weight, 5 to 15% by weight, preferably 6 to 10% by weight, of fatty alcohol alkoxylate and / or 2 to 8, preferably 3 to 5 % by weight of alkyl (poly) glycoside.

5. Liquid detergent according to one of claims 1 to 4, characterized in that, in addition to the nonionic surfactants, the agents contain at least one anionic, preferably at least two anionic surfactants, in particular in a total amount of 15 to 25% by weight, the anionic surfactants are preferably selected from alkylbenzene sulfonates, preferably in amounts of 10 to 25% by weight, preferably 12 to 20% by weight, particularly preferably 14 to 18% by weight, alkyl ether sulfates, preferably in amounts of 2 to 10% by weight, in particular 3 to 8% by weight, and in particular a combination of alkyl benzene sulfonates and alkyl ether sulfates in the specified Amounts.

6. Liquid detergent according to one of claims 1 to 5, characterized in that the surfactant system comprises, based on the total weight of the agent:

(1) at least one alkyl ether, preferably fatty alcohol alkoxylate, preferably in amounts of 5 to 15% by weight, particularly preferably 6 to 10% by weight;

(2) at least one alkyl (poly)glycoside, preferably in amounts of 2 to 8% by weight, preferably 3 to 5% by weight;

(3) at least one alkyl benzene sulfonate, preferably in amounts of 12 to 20% by weight, particularly preferably 14-18% by weight; and

(4) at least one alkyl ether sulfate, preferably in amounts of 2 to 10, particularly preferably 3 to 8% by weight.

7. Liquid detergent according to one of claims 1 to 6, characterized in that the polymeric components are selected from soil-removing polymers (SRP), anti-redeposition agents, color transfer inhibitors (DTI) and polymeric dispersants, the agent preferably containing at least one SRP and optionally at least one DTI .

8. Liquid detergent according to one of claims 1 to 7, characterized in that the agent

(1) contains at least one enzyme; and or

(2) furthermore at least one further component selected from the group consisting of builders, bleaching agents, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, graying inhibitors, shrinkage inhibitors, anti-crease agents, antimicrobial active ingredients, germicides, fungicides, antioxidants, preservatives , corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, softening components, pH adjusting agents and UV absorbers.

9. Use of a liquid detergent according to one of claims 1-8 for washing textiles.

10. A method for cleaning textiles, characterized in that a liquid detergent according to one of claims 1-8 is used in at least one process step.