ES2982982T3 - Fluid concentrated detergent composition with improved properties - Google Patents

Abstract

Fluid detergent preparation containing, based on its total weight, a) 0.1 to 5% by weight of at least one catechol compound of formula (I) wherein R<1> and R<2> independently of each other represent a hydrocarbon radical having 1 to 20 carbon atoms which is optionally substituted by at least one radical selected from hydroxy, (C1-C4)-alkoxy, (C1-C4)-alkoxy(CH2CH2O)n-, -NR'R" or -N<+>R'R"R''' X-, where n = 1 to 10, R', R" and R''' b) 1 to 4.5% by weight of polyalkoxylated polyalkyleneimine, obtainable by the reaction of polyalkyleneimines with alkylene oxides; c) less than 20% by weight of water; detergent portion units comprising this detergent preparation and washing processes using these preparations detergents and detergent serving units. (Automatic translation with Google Translate, no legal value)

Description

DESCRIPTION

Fluid concentrated detergent composition with improved properties

The present invention relates to a highly concentrated detergent composition based on a combination of specific catechol derivatives with polyalkoxylated polyalkylene imines. Furthermore, the application relates to detergent portioning units comprising this detergent composition and to a method for washing textiles using the detergent composition or the detergent portioning unit.

Packaging and delivery requirements for detergents and cleaning agents are constantly changing. For some time now, the main focus has been on convenient dosing of detergents and cleaning agents by the consumer and on simplifying the work steps required for carrying out a washing or cleaning process. One technical solution is pre-dosed detergents or cleaning agents, for example plastic bags with one or more chambers for solid or liquid detergents or cleaning agents. A relevant trend for the production of these film bags is their miniaturisation. In addition to increased consumer acceptance due to simplified handling, the background for this development is primarily sustainability aspects, for example in relation to transport volumes and costs and the amount of packaging materials used.

The concentration of modern detergents, especially modern liquid detergents, often affects their optical and theological properties, impacts the storage stability of these detergents and can affect their cleaning results, especially if the high concentration of active ingredients causes incompatibilities.

International application WO 2020/200600 A1 describes textile detergents containing specific catechol derivatives in combination with mannanase.

International applications WO 2020/074140 A1 and WO 2020/074143 disclose detergents with catechol metal complexes.

The application was based on the task of providing visually attractive, concentrated, free-flowing detergent compositions that are easy and efficient to produce, have a good shelf life and are characterised in particular by good cleaning results. In particular, the detergent composition should be capable of being packaged in water-soluble sachets.

A first object of the application is a fluid detergent composition containing, based on its total weight, a) from 0.1 to 5% by weight of at least one catechol compound of the formula (I)

wherein R1 and R2 independently of each other represent a hydrocarbon radical having from 1 to 20 carbon atoms, which is optionally substituted by at least one radical selected from hydroxy, (C-i-C<4>)-alkoxy, (C<1>-C<4>)-alkoxy(CH<2>CH<2>O)n-, -NR'R" or -N+R'R"R"'X-, where n = 1 to 10, R', R" and R'" independently of each other represent H or a linear or branched aliphatic hydrocarbon radical having from 1 to 3, preferably from 1 to 2 carbon atoms and X- represents an anion;

b) 2 to 3% by weight of polyalkoxylated polyalkyleneimine, which is obtained by reacting polyalkyleneimines with alkylene oxides,

c) less than 20% water by weight.

The detergent composition is fluid under standard conditions (20 °C, 1013 mbar).

A first essential component of the detergent composition is a catechol compound of the formula (I). Preferred detergent compositions contain, based on their total weight, from 0.2 to 2.5% by weight of at least one catechol compound of the formula (I).

Preferably, the catechol compounds of the general formula (I) have a solubility in fully demineralized water of pH 4 at 20 °C of at least 10 mg/l, in particular of at least 20 mg/l.

Preferably, detergent compositions containing at least one catechol compound of the formula (I) wherein the radicals R1 and R2 independently of each other represent an alkyl group (such as methyl, ethyl, n-propyl or i-propyl), an alkoxyalkyl group (such as methoxyethyl, methoxypropyl, (2-methoxy)-ethoxyethyl, ethoxyethyl, ethoxypropyl or (2-ethoxy)-ethoxyethyl), a hydroxyalkyl group (such as 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 1,2-dihydroxypropyl), a hydroxyalkyloxyalkyl group (such as 2-hydroxyethoxyethyl), (N-hydroxyethyl)-aminoethyl, (N-methoxyethyl)-aminoethyl or (N-ethoxyethyl)-aminoethyl, or an aromatic group (such as phenyl or benzyl).

Preferred alkyl groups in formula (I) are linear (C<1>—C<1>ü)-alkyl groups or branched (C<3>—C<1>ü)-alkyl groups, C<5>—C<6>-cycloalkyl.

According to the invention, it is preferable that the radicals R1 and R2 of formula (I) are identical.

Other compounds preferably selected from the group of catechols are at least one compound of the general formula (l—a),

where m and n, independently of each other, represent 0 to 5 and A and B, independently of each other, represent a hydrogen atom, —NR1R2, —N+R1R2R3X—, and R1, R2 and R3, independently of each other, represent H or a linear or branched aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2 carbon atoms, and X" represents an anion.

Among the compounds of the general formula (l—a), those in which A and B are equal are preferred.

X- is preferably selected from the group consisting of lactate, citrate, tartrate, succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, bromide, hydrogen carbonate and carbonate, as well as mixtures of at least two of them, wherein charge equalization in the presence of polyvalent anions can be ensured by the presence of a corresponding number of cationic basic structures of the general formula (I) or optionally by the presence of additional cations such as sodium or ammonium ions. According to the invention, it is preferable if, according to formula (I—a), A and B represent a hydrogen atom.

Highly preferred catechol compounds of formula (I) are compounds of formula (l—b) and/or (l—c), in particular from the group of compounds of formula (l—c)

As a second essential component, the detergent composition contains a polyalkoxylated polyalkyleneimine. Due to their cleaning performance, the detergent compositions according to the invention contain, based on their total weight, 2 to 3% by weight of polyalkoxylated polyalkyleneimine.

Polyalkoxylated polyalkyleneimine is a polymer with a polyalkyleneimine backbone carrying polyalkoxy groups on the N atoms. It preferably has an average molecular weight Mw in the range of 5000 g/mol to 60,000 g/mol, in particular 10,000 g/mol to 22,500 g/mol. The polyalkyleneimine has primary amino functions at the ends and preferably secondary and tertiary amino functions in the interior; if necessary, it can also have only secondary amino functions in the interior, so that a straight-chain rather than a branched polyalkyleneimine is obtained. The ratio of primary to secondary amino groups in the polyalkyleneimine is preferably in the range of 1:0.5 to 1:1.5, in particular in the range of 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkyleneimine is preferably from 1:0.2 to 1:1, in particular from 1:0.5 to 1:0.8. The polyalkyleneimine preferably has a weight average molecular weight of from 500 g/mol to 50,000 g/mol, in particular from 550 g/mol to 2,000 g/mol. The N atoms of the polyalkyleneimine are preferably separated from one another by alkylene groups having 2 to 12 carbon atoms, in particular 2 to 6 carbon atoms, although it is not necessary for all alkylene groups to have the same number of carbon atoms. Particularly preferred are ethylene, 1,2-propylene, 1,3-propylene groups and mixtures thereof. The primary amino functions in the polyalkyleneimine may carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, so that not all amino functions have to be substituted by alkoxy groups. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyalkyleneimine is preferably 5 to 100, in particular 10 to 50. The alkoxy groups in the polyalkoxylated polyalkyleneimine are preferably ethoxy, propoxy or butoxy groups or mixtures thereof. Polyethoxylated polyethyleneimines are particularly preferred. The polyalkoxylated polyalkyleneimines are accessible by reacting the polyalkyleneimines with epoxides corresponding to the alkoxy groups. If desired, the terminal OH function of at least some of the polyalkoxy substituents can be replaced by an alkyl ether function with 1 to 10, in particular 1 to 3 C atoms.

The third essential component of the detergent composition is water, the proportion of which by weight is less than 20% of the total weight of the composition. Due to their high content of active ingredients, the water content of the preferred detergent compositions is less than 15% by weight of water, preferably 2 to 12% by weight and in particular 2 to 10% by weight, based on their total weight.

The solvent system of the detergent composition may be aqueous or aqueous-organic. The use of aqueous-organic solvent systems has proven to be particularly advantageous in terms of manufacturability and shelf life and is therefore preferred.

In a preferred embodiment, the detergent composition contains, based on its total weight, 10 to 35% by weight, preferably 12 to 30% by weight and in particular 15 to 28% by weight of organic solvent. Preferred organic solvents are selected from the group consisting of 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 choleethyl 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, preferably from the group consisting of propanediol, glycerol, ethanol and mixtures thereof.

Preferred detergent compositions contain, based on their total weight, between 30 and 60% by weight, preferably between 35 and 55% by weight and in particular between 40 and 50% by weight of surfactant. The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants. The compositions according to the invention may comprise one or more of the surfactants mentioned. Particularly preferred compositions contain surfactants from the group of anionic and nonionic surfactants.

The anionic surfactant is preferably selected from the group consisting of Cg-C<13> alkylbenzene sulfonates, olefin sulfonates, C<12>-C<18> alkane sulfonates, ester sulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates and mixtures thereof. Compositions including Cg-C-i<3> alkylbenzene sulfonates and fatty alcohol ether sulfates as anionic surfactants have especially good dispersing properties. Preferred sulfonate surfactants are Cg-C-i<3> alkylbenzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained from C<12>-C<18> monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are C<12>-C<18> alkane sulfonates and esters of α-sulfated acids (ester sulfonates), for example α-sulfonated methyl esters of hydrogenated fatty acids from coconut, palm kernel or tallow.

Particularly preferred detergent compositions contain a C<8-18>alkylbenzene sulfonate of the formula (II) as anionic surfactant,

wherein R' and R" are independently H or alkyl and together contain from 8 to 18, preferably from 9 to 15 and in particular from 9 to 13 carbon atoms, and Y+ is a monovalent cation or the nth part of an n-valent cation, in particular monoethanolamine.

The proportion by weight of the anionic surfactant from the group of Ca<-18>alkylbenzenesulfonates in the total weight of the detergent composition is preferably 12 to 30% by weight, preferably 15 to 28% by weight and in particular 18 to 26% by weight.

In addition to the anionic surfactant from the group of C<8-18> alkyl benzene sulfonates, the detergent compositions preferably contain less than 10% by weight, preferably less than 6% by weight and in particular less than 2% by weight of other anionic surfactants, based on their total weight.

Alkalis and in particular the sodium salts of sulfuric acid half-esters of C<12>-C<18> fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of C<10>-C<20> oxoalcohols and of half-esters of secondary alcohols of these chain lengths are preferred as alk(en)yl sulfates. C<12>-C<16>alkyl sulfates and C<12>-C<15>alkyl sulfates as well as C<14>-C<15>alkyl sulfates are preferred for technical reasons. Alkyl 2,3-sulfates are also suitable anionic surfactants.

Preferred alk(en)yl sulphates are the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxoalcohols having 10 to 20 carbon atoms and those half-esters of secondary alcohols of these chain lengths. For technical reasons, alkyl sulphates having 12 to 16 carbon atoms and alkyl sulphates having 12 to 15 carbon atoms as well as alkyl sulphates having 14 and 15 carbon atoms are preferred. Alkyl 2,3-sulphates are also suitable anionic surfactants.

Also suitable are fatty alcohol ether sulfates, such as sulfuric acid monoesters of ethoxylated straight-chain or branched C<7>-C<21> alcohols with 1 to 6 mol of ethylene oxide, such as C<9-11>2-methyl-branched alcohols with an average of 3.5 mol of ethylene oxide (EO) or C<12-18> fatty alcohols with 1 to 4 EO. Alkyl ether sulfates of the formula (III-A) are preferred.

R1-O-(AO)n-SO3-X+ (Mi-a)

In this formula (lll-a), R1 is a linear or branched alkyl radical, substituted or unsubstituted, preferably an unsubstituted linear alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R1 of the formula (A-1) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with representatives with an even number of carbon atoms being preferred. Particularly preferred radicals R1 of the formula (lll-a) are derived from fatty alcohols having 12 to 18 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxoalcohols having 10 to 20 carbon atoms.

In formula (lll-a), AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n of formula (A-1) is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is particularly preferred 2, 3, 4, 5, 6, 7 or 8. X is a monovalent cation or the nth part of an n-valent cation, with alkali metal ions including Na+ or K+ being preferred, with Na+ being extremely preferred. Other cations X+ may be selected from NH<4>+, A Zn2+,A Mg2+,A Ca2+,A Mn2+, and mixtures thereof.

Preferred compositions contain an alkyl ether sulfate selected from the fatty alcohol ether sulfates of the formula (lll-b)

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Particularly preferred representatives are the Na fatty alcohol ether sulphates with 12 to 18 C atoms and 2 EO (k = 11 to 13, n = 2 in formula A-1). The stated degree of ethoxylation represents a statistical mean value, which may be an integer or fractional number for a specific product. The stated degrees of alkoxylation represent statistical means, which may be an integer or fractional number for a specific product. Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

In a particularly preferred embodiment, the detergent composition contains, based on its total weight, less than 10% by weight, preferably less than 6% by weight and in particular less than 2% by weight of anionic surfactant from the group of alkyl ether sulphates.

In another technically advantageous variant, the detergent composition contains, based on its total weight, 12 to 30% by weight, preferably 15 to 28% by weight and, in particular, 18 to 26% by weight of nonionic surfactant. Preferred nonionic surfactants are selected from the group of ethoxylated Cs<-18> primary alcohols, preferably ethoxylated C<8-18> primary alcohols with a degree of alkoxylation > 4, particularly preferred are C<12-14> alcohols with 4 EO or 7 EO, C<9-11> alcohols with 7 EO, C<13-15> alcohols with 5 EO, 7 EO or 8 EO, C<13-15> oxoalcohols with 7 EO, C<12-18> alcohols with 5 EO or 7 EO, in particular C<12-18> fatty alcohols with 7 EO or C<13-15> oxoalcohols with 7 EO.

With regard to the theological properties of the detergent composition, its processability and its cleaning effect, it has been proven to be advantageous to use anionic surfactant and nonionic surfactant in a weight ratio of 2:1 to 1:2, preferably 3:2 to 2:3.

The use of fatty acids has proven to be advantageous for stability and cleaning performance. Preferred detergent compositions therefore contain, based on their total weight, 4 to 12% by weight, preferably 6 to 10% by weight of fatty acid. Particularly preferred fatty acids are selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and mixtures thereof. In the context of the application, fatty acids are assigned to the group of anionic surfactants.

Preferred detergent compositions contain phosphonate as an optional component. The proportion by weight of the phosphonate in the total weight of the detergent composition is preferably from 0.1 to 3% by weight and, in particular, from 0.2 to 1% by weight.

The phosphonate compound is preferably a phosphonate selected from the group of fluoroalkyl and/or aminoalkane phosphonates, preferably from the group of aminoalkane phosphonates and in particular from the group of ethylenediaminetetramethylene phosphonate (EDTMP) and diethylenetriaminepentamethylene phosphonate (DTPMP). Preferred detergent compositions additionally contain 0.5 to 10% by weight, preferably 2 to 8% by weight, of a polyalkoxylated amine with a weight average molecular weight Mw in the range of 600 g/mol to 10,000 g/mol, which is obtained by reacting ammonia or primary alkylamines or hydroxyalkylamines, having a molecular weight of less than 200 g/mol, with alkylene oxides. Corresponding weight ratios have proven to be advantageous for pot life, but especially for cleaning performance.

Particularly preferred polyalkoxylated amines have a weight average molecular weight Mw of between 1300 g/mol and 6000 g/mol, in particular between 1400 g/mol and 4500 g/mol. (The average molecular weights stated here and below for other polymers are weight average molecular weights Mw, which can in principle be determined by gel permeation chromatography with the aid of an Rl detector, the measurement being conveniently carried out against an external standard.) For its preparation, it is possible to use ammonia, a monoalkylamine, a monoalkyl-monoalkanolamine or a monoalkyl-dialkanolamine or a mono-, di- or trialkanolamine, for example triethanolamine, in a known manner, methyl-, ethyl-, propyl- and isopropyl-diethanolamine, methyl-, ethyl-, propyl- and isopropyl-diisopropanolamine, tripropanolamine, triisopropanolamine, N,N-di-(2-hydroxyethyl)cyclohexylamine, N,N-di-(2-hydroxypropyl)cyclohexylamine, n-butylamine, n-hexylamine, n-octylamine, isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, 2-ethylhexylamine, 2-phenylethylamine and mixtures thereof, which is reacted with an alkylene oxide, in particular selected from the group consisting of ethylene, propylene oxide, butylene oxide and mixtures thereof, in particular with a mixture comprising propylene oxide and preferably ethylene oxide, particularly preferably with propylene oxide. The polyalkoxylated amines thus obtained can be block or random structures. Particularly preferred, among others, is a polyalkoxylated amine obtainable by propoxylation of triethanolamine, preferably with a length of the three lateral arms of 15 propylene oxide units each. Also preferred is a polyalkoxylated amine, obtainable by propoxylation of triisopropanolamine, preferably with a length of the three lateral arms of 15 propylene oxide units each. Also suitable are polyalkoxylated monoalkylamines with a linear, branched or cyclic alkyl group, in which the alkoxylation is carried out with an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide. Also preferred is a polyalkoxylated amine obtainable by propoxylation of tert-butylamine, preferably with a length of the two side arms of 12 propylene oxide units each.

The preferred polyalkoxylated amines correspond to the general formula (IV),

wherein R represents a linear, optionally branched or optionally cyclic alkyl group having 1 to 12 carbon atoms or a group -(CH<2>CHR'O)n»-(CH<2>CHR"O)m"-H,

R' and R" independently of each other represent H, CH<3>or CH<2>CH<3>,

n, n' and n" independently of each other represent numbers from 0 to 30, preferably from 0 to 10 and in particular from 0 to 5, and m, m' and m" independently of each other represent numbers from 0 to 30, preferably from 5 to 20 and in particular from 12 to 16,

with the proviso that the sum n n' n" m m' m" is at least 14, preferably in the range from 18 to 100 and in particular in the range from 20 to 70. Preferably, in the compounds of formula I at least one of the radicals R' and R" is a CH<3> group.

Due to their improved cleaning effect, detergent compositions containing 2 to 8% by weight, preferably 3 to 6% by weight of enzyme composition as an additional optional component are preferred.

In addition to the enzyme protein itself, an enzyme composition comprises other components such as enzyme stabilizers, support materials or fillers. The enzyme protein usually constitutes only a fraction of the total weight of the enzyme composition. Preferably, the enzyme compositions used contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight, and most preferably between 0.8 and 10% by weight of the enzyme protein. In such compositions, an enzyme stabilizer may be present in an amount of from 0.05 to 35% by weight, preferably from 0.05 to 10% by weight, based on the total weight of the enzyme composition.

The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method. The active protein concentration is determined by titration of the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity.

It is preferable that the detergent composition further comprises at least one enzymatic composition, preferably at least 3 enzymatic compositions of enzymes from the group consisting of lipase, amylase, protease, cellulase, prepared from a pectinolytic enzyme and endoglucanase.

According to the invention, it is preferable that the detergent composition contains at least one lipase composition. Preferred lipases according to the invention are selected from at least one enzyme from the group consisting of triacylglycerol lipase (C.E. 3.1.1.3), and lipoprotein lipase (C.E. 3.1.1.34) and monoglyceride lipase (C.E. 3.1.1.23).

Preferred lipase compositions according to the invention are the commercial products marketed by Amano Pharmaceuticals under the names Lipase M-AP 10®, Lipase LE® and Lipase F® (also Lipase JV®). Lipase F®, for example, is naturally present in Rhizopus oryzae. Lipase M-AP10® is naturally present in Mucor javanicus, for example.

A highly preferred lipase is commercially available under the trade name Lipex® from Novozymes (Denmark) and can be advantageously substituted in the detergent preparations according to the invention. Lipex® 100 L lipase is particularly preferred.

Preferred detergent compositions are characterized in that they contain, based on their total weight, from 0.01 to 1% by weight, in particular from 0.05 to 0.3% by weight, of lipase composition.

Detergent compositions preferably contain at least one amylase, in particular an α-amylase. α-Amylases (C.E. 3.2.1.1) are enzymes which hydrolyse the internal α-1,4-glycosidic bonds of starch and starch-like polymers. Examples are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens and B. stearothermophilus and their improved further developments for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the trade name Termamyl® and from Genencor under the trade name Purastar®ST. Further development products of these α-amylases are offered by Novozymes under the trade names Duramyl® and Termamyl®ultra, by Genencor under the name Purastar®OxAm and by Daiwa Seiko Inc. of Tokyo, Japan under the name Keistase®. α-Amylase from B. amyloliquefaciens is marketed by Novozymes under the trade name BAN®, and variants derived from α-amylase from B. stearothermophilus are marketed under the trade names BSG® and Novamyl®, also from Novozymes. Examples of α-amylases from other organisms are the later developments of α-amylase from Aspergillus niger and A. oryzae available under the trade names Fungamyl® from Novozymes.

The proportion by weight of the amylase composition, in particular of the α-amylase composition, in the total weight of the detergent composition is preferably 0.1 to 2% by weight, in particular 0.2 to 1% by weight.

According to the invention, it is preferable that the detergent composition contains at least one protease as an enzyme. A protease is an enzyme which cleaves peptide bonds by hydrolysis. According to the invention, each of the enzymes of class E.C. 3.4 is included therein (each comprising thirteen subclasses included therein). According to the invention, there is "protease activity" if the enzyme has proteolytic activity (EC 3.4). Different types of protease activity are known: The three main types are: Trypsin-type, where the cleavage of the substrate amide occurs after the amino acids Arg or Lys in P1; Chymotrypsin-type, where the cleavage occurs after one of the hydrophobic amino acids in P1; and Elastase-type, where the cleavage of the substrate amide occurs after Ala in P1.

Surprisingly, it was found that a protease of the alkaline protease type from Bacillus lentus DSM 5483 or a sufficiently similar protease (in terms of sequence identity), having several of these modifications in combination, is particularly suitable for use in the detergent compositions according to the invention and is advantageously stabilised therein in an improved manner. The use of this protease thus presents advantages, in particular as regards washing performance and/or stability.

More preferably, the detergent composition according to the invention contains protease of the alkaline protease type of Bacillus lentus DSM 5483 or a protease sufficiently similar thereto (in terms of sequence identity), which has several of these modifications in combination,

The proportion by weight of the protease composition in the total weight of the detergent composition is preferably 0.5 to 5% by weight, in particular 1.0 to 4% by weight.

Preferred detergent compositions further contain as an optional component, based on their total weight, from 0.05 to 2% by weight, preferably from 0.1 to 0.4% by weight, of a pectinolytic enzyme preparation. In the context of the present invention, pectinolytic enzymes include enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectin pectyl hydrolase, pectin depolymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin polygalacturonase, endo-polygalacturonase, poly-α-1,4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4-α-galacturonidase, exopolygalacturonase, poly(galacturonate) hydrolase, exo-D-galacturonase, exo-D-galacturonanase, exopoly-D-galacturonase, exo-poly-galacturonosidase, exopolygalacturonosidase or exopolygalacturonosidase. The use of pectate lyases is especially preferred.

Within the EC classification of enzymes, the numerical classification system for enzymes, pectinolytic enzymes belong in particular to the enzyme classes EC 3.1.1.11, EC 3.2.1.15, EC 3.2.1.67 and EC 3.2.1.82 and therefore belong to the third of the six main enzyme classes, the 10 hydrolases (EC 3.1.1.11, EC 3.2.1.15, EC 3.2.1.67 and EC 3.2.1.82) including glycosylases (EC 3.2.1.1) and again glycosidases (EC 3.2.1.1), i.e. enzymes which hydrolyse O- and/or S-glycosylated compounds. Pectinolytic enzymes therefore act in particular against dish residues containing pectic acid and/or other galacturonans and catalyse their hydrolysis.

Pectate lyases within the meaning of the invention are enzymes which catalyse the non-hydrolytic cleavage of pectate according to an endomechanism.

Examples of suitable pectinolytic enzymes are those marketed under the trade names Gamanase®, Pek- tinex AR®, X-Pect® or Pectaway® by Novozymes, under the trade names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1L® by AB Enzymes and under the trade name Pyrolase® by Diversa Corp., San Diego, CA, USA.

As a preferred component, the detergent composition contains 0.01 to 1% by weight, preferably 0.02 to 0.3% by weight of a mannanase composition.

A mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and galactoglucomannans. These mannanases are classified as C.E. 3.2.1.78 according to the enzyme nomenclature.

The xanthanases and mannanases characterizing the subject matter of the claim are preferably components of a more complete enzyme system. In a preferred embodiment, due to its improved cleaning performance, the detergent composition further comprises, in addition to the xanthanase and mannanase composition, 2 to 8% by weight, preferably 3 to 6% by weight of enzyme composition, based on its total weight.

As a further preferred optional component, the detergent compositions contain a cellulase composition. Synonymous terms for cellulases may be used, in particular endoglucanase, endo-1,4-beta-glucanase, carboxymethylcellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucanohydrolase, celludextrinase or avicelase. The decisive factor in determining whether an enzyme is a cellulase within the meaning of the invention is its ability to hydrolyze 1,4-13-D-glucosidic bonds in cellulose.

Suitable cellulases according to the invention (endoglucanases, EG) include, for example, compositions rich in fungal endoglucanase (EG), which are offered by Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from Humicola insolens DSM 1800, respectively. Other replaceable commercial products from this company are Cellusoft®, Renozyme® and Celluclean®. Cellulases from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, which are based, at least in part, on the 20 kD EG from Melanocarpus, can also be used. Other cellulases from AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are those from Bacillus sp. CBS 670.93 and CBS 669.93. Bacillus sp. cellulase CBS 670.93 is available from Danisco/Genencor under the trade name Puradax®. Other commercial Danisco/Genencor products that can be used are "Genencor detergent cellulase L" and IndiAge®Neutra.

The weight proportion of the cellulase composition in the total weight of the detergent composition is preferably 0.01 to 1% by weight, preferably 0.05 to 0.3% by weight.

As an additional optional component, a preferred detergent composition comprises 0.2 to 4% by weight, preferably 0.5 to 3% by weight of fragrance composition.

In addition to the fragrances themselves, the fragrance composition includes, for example, solvents, solid carrier materials or stabilizers.

A fragrance is a chemical substance that stimulates the sense of smell. In order to stimulate the sense of smell, the chemical substance must be at least partially dispersible in the air, i.e. the fragrance must be at least slightly volatile at 25 °C. If the fragrance is highly volatile, the odour intensity will decrease rapidly. If the fragrance is highly volatile, the odour intensity will decrease rapidly. However, with lower volatility, the odour impression is longer lasting, i.e. it does not disappear as quickly. In one embodiment, the fragrance has a melting point between -100 °C and 100 °C, preferably between -80 °C and 80 °C, and even more preferably between -20 °C and 50 °C, in particular between -30 °C and 20 °C. In another embodiment, the fragrance has a boiling point between 25 °C and 400 °C, preferably between 50 °C and 380 °C, more preferably between 75 °C and 350 °C, in particular between 100 °C and 330 °C.

In general, a chemical should not exceed a certain molecular mass to function as a fragrance, since the required volatility cannot be guaranteed if the molecular mass is too high. In one embodiment, the fragrance has a molecular mass of 40 to 700 g/mol, more preferably 60 to 400 g/mol.

The smell of a fragrance is perceived as pleasant by most people and usually corresponds to the smell of flowers, fruits, spices, bark, resin, leaves, herbs, mosses and roots, for example. Fragrances can also be used to mask unpleasant odours or to give a non-odorous substance its odour. Individual odorous compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as fragrances.

Preferably, mixtures of different fragrances are used, which together create an attractive aroma. Such a fragrance mixture may also be called perfume or perfume oil. Such perfume oils may also contain mixtures of natural fragrances, such as those available from plant sources.

It has proven to be advantageous to encapsulate the fragrance in order to prolong its effect. In a corresponding embodiment, at least a part of the fragrance is used in encapsulated form (fragrance capsules), in particular in microcapsules. However, the entire fragrance can also be used in encapsulated form. The microcapsules can be water-soluble and/or water-insoluble. For example, melamine-urea-formaldehyde microcapsules, melamine-formaldehyde microcapsules, urea-formaldehyde microcapsules or starch microcapsules can be used. "Fragrance precursor" refers to compounds that release the actual fragrance only after chemical conversion/removal, usually by exposure to light or other environmental conditions such as pH, temperature, etc. These compounds are also often referred to as fragrance storage substances or "profragrances".

The composition of some fluid detergent compositions can be obtained from the following tables (weight % figures based on the total weight of the composition, unless otherwise indicated). The detergent compositions are preferably packaged as detergent portion units in which the composition

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The detergent composition can be packaged in the form of single-dose units, but also in larger containers. In addition to transparent plastic bottles, transparent bags, in particular transparent water-soluble bags, are used for packaging.

Another object of the present application is a detergent portioning unit comprising

i) a detergent composition according to the invention

ii) a water-soluble film that completely envelops the detergent composition.

The water-soluble film in which the detergent composition is packaged may comprise one or more structurally different water-soluble polymers. Polymers from the group of polyvinyl alcohols (optionally acetalized) (PVAL) and their copolymers are particularly suitable as water-soluble polymers.

Water-soluble films 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 gmol-1, preferably 20,000 to 500,000 gmol-1, particularly preferably 30,000 to 100,000 gmol-1 and especially 40,000 to 80,000 gmol-1.

The production of polyvinyl alcohol and polyvinyl alcohol copolymers typically involves the hydrolysis of intermediate polyvinyl acetate. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol %, and especially 82 to 88 mol %.

Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. In addition to vinyl alcohol, such polyvinyl alcohol copolymers particularly preferably contain sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof; among the esters, Ci<-4>-alkyl esters or hydroxyalkyl esters are preferred. Other suitable monomers are ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid and mixtures thereof.

Suitable water-soluble films are marketed by MonoSol LLC, for example under the designation M8630, M8720, M8310, Cs400 or M8900. Other suitable films are Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbHFI or VF-FIP films from Kuraray.

Water-soluble films may contain additional active ingredients or fillers, as well as plasticizers and/or solvents, especially water.

The group of other active substances includes, for example, materials that protect the ingredients of the composition enclosed by the film material from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable in this case.

For example, glycerol, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, sorbitol or mixtures thereof can be used as plasticizers.

To reduce their coefficients of friction, the surface of the water-soluble film of the detergent portioning unit can optionally be dusted with a fine powder. Sodium aluminosilicate, silicon dioxide, talc and amylose are examples of suitable dusting agents.

Preferred water-soluble films are suitable for processing in a thermoforming apparatus.

The volume of the detergent portioning unit is preferably 12 to 28 ml, particularly preferably 14 to 25 ml.

Preferred detergent portioning units have one to four receiving chambers, preferably three or four receiving chambers.

Another object of the application is a process for cleaning textiles, wherein a detergent preparation unit or detergent portion described above is introduced into the wash liquor of a textile washing machine.

In preferred process variants, the detergent composition or the detergent portioning unit is metered directly into the drum or rinse drawer of the textile washing machine.

The automated textile washing process is preferably carried out at temperatures of 20 °C to 60 °C, preferably 30 °C to 45 °C.

Examples

The fabrics were treated with standard soiling and washed at 40 °C in washing solutions containing 1 g/l of a detergent V1, V2, V3 or E1. After washing, the fabrics were dried. The brightness values of the washed textiles were determined. The values stated were the average values of five washing tests.

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Table 2: Differences in luminosity values Y values

Claims (9)

CLAIMS 1. Fluid detergent composition containing, based on its total weight a) from 0.1 to 5% by weight of at least one catechol compound of formula (I) where R1 and R2 independently of each other represent a hydrocarbon radical having 1 to 20 carbon atoms, which is optionally substituted by at least one radical selected from hydroxy, (C<1>-C<4>)-alkoxy, (C<1>-C<4>)-alkoxy(CH<2>CH<2>O)n-, -NR'R" or -N+R'R"R'"X- , where n = 1 to 10, R', R" and R'" independently of each other represent H or a linear or branched aliphatic hydrocarbon radical having 1 to 3, preferably 1 to 2 carbon atoms and X- represents an anion; b) 2 to 3% by weight of polyalkoxylated polyalkyleneimine, which is obtained by reacting polyalkyleneimines with alkylene oxides, c) less than 20% water by weight. 2. Detergent composition according to claim 1, wherein the detergent composition contains, based on its total weight, 0.2 to 2.5% by weight of at least one catechol compound of the formula (I). 3. Detergent composition according to one of the preceding claims, wherein the at least one catechol compound of the formula (I) is selected from the group of compounds of formulae (l-b) and (l-c), in particular from the group of compounds of the formula (l-c) 4. Detergent composition according to one of the preceding claims, wherein the polyalkoxylated polyalkyleneimine has a weight average molecular weight Mw in the range of 5000 g/mol to 60,000 g/mol, in particular 10,000 g/mol to 22,500 g/mol. 5. Detergent composition according to one of the preceding claims, wherein the detergent composition contains a polyethoxylated polyethyleneimine such as polyalkoxylated polyalkyleneimine. 6. Detergent composition according to one of the preceding claims, wherein the detergent composition contains, based on its total weight, 30 to 60% by weight, preferably 35 to 55% by weight and, in particular, 40 to 50% by weight of surfactant. 7. Detergent composition according to one of the preceding claims, wherein the detergent composition contains, based on its total weight, less than 15% by weight of water, preferably 2 to 12% by weight and, in particular, 2 to 10% by weight of water. 8. Detergent portioning unit comprising i) a detergent composition according to any of claims 1 to 7, ii) a water-soluble film completely enveloping the detergent composition. 9. Process for cleaning textiles, wherein a detergent composition according to one of claims 1 to 7 or a detergent portioning unit according to claim 8 is introduced into the wash liquor of a textile washing machine.