CZ43099A3 - Detergents containing pectolytic enzymes being active in basic medium - Google Patents

Abstract

The present invention relates to detergent compositions, including dishwashing, hard surface cleaning and laundry compositions containing an alkaline pectin degrading enzyme for improved overall cleaning performance and enhanced stain/soil removal benefits and in particular improved removal of plant, dried-on fruit and vegetable juice soils/stains.

Description

Detergents with pectolytic enzymes active in an alkaline environment

Field of technology

This invention relates to detergents, including dishwashing preparations, solid surface cleaning preparations and laundry preparations, containing a pectolytic enzyme active in an alkaline environment.

Current state of the art

Food-borne impurities are often difficult to remove from contaminated objects. Removing highly colored or dried-on dirt that comes from fruit and/or vegetable juices is sometimes particularly difficult. Examples of such impurities are impurities from orange juice, tomato juice, banana, mango or broccoli juice. Contaminated objects can be textiles, dishes or hard surfaces.

Pectins are contained, for example, in fruit juices. The pectins cause the particles to be dispersed in these juices in a suspension, which therefore has a viscous and cloudy character. Pectolytic enzymes are usually used in the processing of fruit and vegetable juices to clarify them by breaking down the pectins contained in them (depectinization).

Pectolytic enzyme has also been found to be suitable for cleaning contact lenses (US Patent No. 4,710,313 J60196724).

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The document DE 36 35 427 describes the use of enzymes with pectolytic activity to increase the detergent's ability to remove impurities of an inorganic nature, for example sludge, produced during washing, without damaging the fibers and without discolouration, in order to enable the use of zeolite and polycarbonate auxiliary components which have lower ability to disperse inorganic materials than phosphates. Document W095/25790 shows that it is advantageous to use pectolytic enzymes in detergents, especially in laundry detergents, in dishwashing preparations and in household cleaning preparations. In the document

JP 60226599 describes a detergent containing common detergent active substances, cellulose and hydrolases such as hemiellolulase, pectinase, amylase or protease. According to available information, the combination of cellulase and hydrolase has good efficiency and enzymatic activity.

Document WO95/09909 describes an enzyme composition comprising a modified enzyme selected from the group consisting of amylases, lipases, oxidoreductases, pectinases or hemicellulases, wherein this modified enzyme has improved efficiency due to alkaline pH and/or increased surface activity * obtained by chemical modification or amino acid replacement . Modified pectin and/or pectolytic and/or hemicellulolytic and/or lipolytic enzymes are successfully used in the paper industry, and modified amylase and/or lipase, * in washing and as part of dishwashing preparations.

The essence of the invention

The object of the present invention is to provide a washing powder, dishwashing agent or detergent used in the home

9 9 99 9

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9999 999 99 9 99 99 with improved ability to remove dirt and stains when used in washing and cleaning.

According to this invention, it has now surprisingly been found that pectolytic enzymes with an enzymatic activity of at least 10%, preferably 25%, more preferably 44% of their optimal activity, at an OH in the range from 7 to 11, and in particular a pectolytic enzyme with an optimal activity at an OH in the range from 7 to 11, significantly improve the removal of a large amount of impurities originating from plants and fruits and improve the cleaning ability of the detergents in which they are contained.

By using a pectolytic enzyme active in an alkaline environment, there is a significant improvement in the ability to remove dried impurities originating from fruit and vegetable juices or stains of the same origin.

Furthermore, pectolytic enzyme active in an alkaline environment has been found to be the cause of improved compatibility and increased activity in the washing solution and, as a result, improves the ability to remove dried residues of fruit and vegetable juices, especially when it is part of washing powders or dishwashing preparations. It has also been found that pectolytic enzyme active in an alkaline environment is characterized by better compatibility with the detergent matrix, for example during production and storage.

Furthermore, it was also surprisingly found that the use of dispersants, especially these agents based on organic polymers, is very advantageous in detergents containing pectolytic enzymes active in an alkaline environment. With the help of these dispersants, the decomposition products of the enzymatic degradation of impurities are dispersed and thus their re-deposition on the objects being cleaned is prevented.

Improved cleaning efficiency has also been observed for combinations of pectolytic enzymes active in an alkaline environment with other enzymes that are used as components of detergents. Enzymatic bleaching systems or conventional activated bleaching systems, in the presence of pectolytic enzymes active in an alkaline environment, provide increased efficiency on a wide range of impurities.

Polymers that inhibit dye transfer further provide improved whiteness and/or improved soil removal efficiency in combination with pectolytic enzymes active in an alkaline environment.

Brief description of the invention

This invention relates to detergents, including preparations for washing dishes, preparations for cleaning hard surfaces and laundry preparations, containing a pectolytic enzyme active in an alkaline environment in order to improve the overall cleaning efficiency and especially for more effective removal of dried dirt and stains from plant and vegetable juices.

In a preferred embodiment of the present invention, the detergent according to the present invention also contains a dispersing agent, a bleaching system, an additional enzyme and/or dye transfer inhibiting polymer.

Detailed description of the invention

Pectolytic enzyme active in an alkaline environment

The basic component of the detergents according to this invention is a pectolytic enzyme active in an alkaline environment. According to this document, a pectolytic enzyme is any enzyme capable of breaking down pectins and pectin-like substances. Pectins are found in plant cell tissues and are common components of fruit juices such as orange juice, tomato juice, and grapefruit juice. Pectins contain galacturonic acids and/or their derivatives.

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The term active in an alkaline environment means a pectolytic enzyme with an enzymatic activity of at least 10%, preferably 25%, more preferably 40% of optimal activity, at a pH in the range from 7 to 11, and preferably a pectolytic enzyme with an optimal activity at a pH in the range from 7 to 11 , Enzymatic activity can be measured as described in the publication Measurement of viscosity by K. Horikoshi, Agr. Biol. Chem., 36(2), 286,

The term pectolytic enzyme means polygalacturonase (EC 3.2.1.15), exo-polygalacturonase (EC 3.2.1.67), exo-poly-agagalacturonidase (EC 3.2.1.82), pectinlyase (EC 4.2.2.10), pectinesterase (EC 3.2.1.11), pectate lyase (EC 4.2.2.2), exopolygalacturonate lyase (EC 4.2.2.9) and hemicellulases such as endo1,3-p-xylosidase (EC 3.2.1.32), xylan-1,4-p~xylosidase (EC 3.2.1.37) and α- L-arabinofuranosidase (EC 3.2.1.55). Pectolytic enzymes active in an alkaline environment are mixtures of the above-mentioned enzymatically active substances.

Pectolytic enzymes are therefore pectin methylesterases that hydrolyze methyl ester bonds, polygalacturonases that cleave glycosidic bonds between galacturonic acid molecules, and pectin transeliminases or lyases that act on pectic acids by causing non-hydrolytic cleavage of α-1-glycosidic bonds to form unsaturated galacturonic acid derivatives.

Pectin substances are pectins and pectic acids. Pectins are generally polymers made up of galacturonic acid chains linked by α-1→4-glycosidic bonds. In natural pectins, usually two-thirds of the carboxyl groups are esterified with methanol. The product of partial hydrolysis of these methyl esters is lower methoxypectins, which readily form gels by reaction with calcium ions. Complete hydrolysis of esters produces pectic acids.

- 6 The pectolytic enzyme phenomenon in detergents according to this invention is preferably contained in concentrations of 0.0001 to 2 wt.%, more preferably 0.0005 to 0.5 wt.%, most preferably 0.001 to 0.1 wt.%. % of pure enzyme, based on the total weight of the detergent.

The pectolytic enzyme can be produced by so-called "wild" microorganisms or any microorganisms in which the gene responsible for the production of the pectolytic enzyme is cloned.

Pectolytic enzymes active in an alkaline environment are produced by alkalophilic microorganisms, for example bacteria, fungi or yeasts such as bacillus type microorganisms. Preferred microorganisms are bacillus firmus, bacillus circulans and bacillus subtilis described in documents JP 56131376 and JP 56068393. Pectolytic enzymes active in an alkaline environment are galacturan-1,4-α-galacturonase (EC 3.2.1.67), poly-galacturonase (EC 3.2. 1.15), pectinesterase (EC 3.1.1.11), pectate lyase (EC 4.2.2.2) and relevant isoenzymes. These enzymes can be produced by microorganisms of the erwinia type. Preferred are E. chrysanthemi, E. carotovora, E. amylovora, E. herbicola and E. dissolvens described in documents JP 59066588, JP 63042988 and in the publication World J. Microbiol. Microbiotechnol. 8, 2, 115-120 (1992). As stated in the document JP 73006557 and in the publication Agr. Biol. Chem., 36(2) 285-93, (1972), the mentioned pectolytic enzymes active in an alkaline environment can also be produced by microorganisms of the bacillus type.

It is currently common practice to modify wild-type enzymes in the detergent compositions of the present invention by protein genetic engineering techniques in order to optimize their effectiveness. Different variants can be chosen to increase the compatibility of the enzyme with the components usually present in these compositions. Another possibility is that a variant of the microorganism is chosen which provides the appropriate modified enzyme with optimal resistance against · 99 99

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9 9 9 9 99 decolorization, and optimal catalytic activity of the respective enzyme, corresponding to its use in a certain cleaning product.

Particular attention should be paid to oxidation-sensitive amino acids in case of a requirement for fastness against discoloration and to surface tension to achieve surfactant compatibility. The isoelectric point of such enzymes can be influenced by replacing some charged amino acids. For example, raising the isoelectric point can help improve compatibility with anionic surfactants. The stability of enzymes can be further increased, for example, by creating additional salt bridges, and by strengthening the calcium binding sites, resistance to chelating agents can be increased.

Dispersants

It was also surprisingly found that for detergents containing pectolytic enzymes active in an alkaline environment, the addition of dispersants, especially organic polymers, is very advantageous. These dispersants help disperse decomposition products resulting from the enzymatic decomposition of impurities and thus prevent their re-deposition on the objects being cleaned.

Suitable water-soluble organic salts are homo- or copolymeric acids or their salts, in which the polycarboxylic acid contains at least two carboxyl groups that are separated from each other by no more than two carbon atoms.

Polymers of this type are described in GB-A-1 596 756. Examples of such salts are polyacrylates having a molecular weight of 2000 to 5000 and their copolymers with maleic anhydride having a molecular weight of 1000 to 100,000.

A copolymer of acrylate and methacrylate, such as copolymer • · • · · · · · · · · · · · · · ·' · • · · ·· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ······ ··· • · · · · · ···· ··· · · · · ·

480N with a molecular weight of 4000, in a concentration of 0.5 to 20% by weight, based on the total weight of the product.

Preparations according to this invention can contain a lime soap peptizer with a value further defined by the dispersing power for calcium salts (lime soap dispersing power - LSDP), a maximum of 8, preferably a maximum of 7, most preferably 6. The concentration of this lime soap peptizer is preferably 0 to 20 wt. .%

A quantitative measure of the effectiveness of a lime soap peptizer is given by the lime soap dispersing power (LSDP), which is determined using the lime soap dispersion test described in H.C. Borghetti, C.A. Bergman: J. Am. Oil. Chem. Soc., vol. 27, pp. 88-90, (1950). The use of this lime soap dispersion test is widespread among those skilled in the art and is mentioned, for example, in the following review articles: W.N. Linfield, Surfactant Science Series, Vol. 7, p. 3; W. N. Linfield, Tenside surf. det., vol. 27, pp. 159-163, (1990); and M.K. Nagarajan, W.F.

Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73, (1989). The LSDP value is expressed in the ratio of dispersant to sodium oleate, which is needed to disperse lime soap deposits formed from 0.025 g of sodium oleate in 30 ml of water with a hardness corresponding to 333 ppm CaCO ₃ (Ca:Mg = 3:2).

Surfactants that are effective calcium soap peptizers are some amine oxides, betaines, sulfobetaines, alkylethoxysulfate and ethoxylated alcohols.

Examples of surfactants with an LSDP value of at most 8 suitable for use in the processes of the present invention are C16-C18 dimethylamine oxides, Ci ₂ -Ci ₈ alkyl ethoxysulfates with an average degree of ethoxylation of 1-5, especially C12-C15 alkyl ethoxysulfate surfactants with a degree ethoxylation 3 (LSDP=4) and C14-C15 ethoxylated alcohols with an average degree

- 9 ethoxylation either 12 (LSDP=6) or 30, produced under the trade names Lutensol A012 and Lutensol A030 by BASF GmbH.

Polymeric soap peptizers suitable for use in the processes of this invention are described in M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73, (1989).

Hydrophobic bleaching agents such as 4-[N-octanoyl-aminohexanoyl]benzenesulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzenesulfonate, 4-[N-decanoyl-6-aminohexanoyl]benzenesulfonate can also be used as lime soap peptizers and mixtures thereof, and nonanoyloxybenzenesulfonate, together with hydrophilic/hydrophobic bleaching agents.

Detergent enzymes

Improved removal of large quantities of stains originating from plant material or fruit is achieved by combining alkaline-active pectolytic enzymes with other detergent enzymes.

A synergistic effect can be observed with detergents containing a pectolytic enzyme active in an alkaline environment and cellulase, xylanase and/or protease.

Celluloses of bacterial origin as well as cellulases produced by fungi can be used in the procedures according to the present invention. The optimal pH for the action of these enzymes is preferably 5 to 9.5. Suitable cellulases are described in US patent no. 4,435,307, by Barbesgoard et al., in which a fungal cellulase produced by Humicola insolens is described. Suitable cellulases are also described in GB-A-2 075 028 and GB-A-2 095 275 and in DE-OS-2 247 832.

Examples of such cellulases are cellulases produced by the strain

Humicola insolens (Humicola grisea var. thermoidea), especially the strain Humicola DSM 1800. Other suitable cellulases are

cellulases from Humicola insolens with a molecular weight of about 50 kDa and an isoelectric point of 5.5, containing 415 amino acids. Particularly suitable cellulases are cellulases that have advantageous properties in terms of preserving the color fastness of washed textiles. Examples of such cellulases are those described in European Patent Application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are particularly suitable. See also WO91/17243.

Suitable xylanases are industrially produced xylanases such as Pulpzyme HS and 5P431 (Novo Nordisk), Lyxasan (Gist-Brocades), Optipulp and Xylanase (Solvay).

Suitable proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). A suitable protease is a protease obtained from a bacillus strain, with maximum activity in the pH range of 8-12, obtained and sold under the name ESPERASE by the Danish company Novo Industries A/S, which is referred to as Novo in the following text. The preparation of this enzyme and analogous enzymes is described in GB 1,243,784, granted to Novo. Other suitable proteases are ALCALASE®, DURAZYM® and SAVINASE® produced by Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal obtained by gene manipulation) produced by the Dutch company International Bio-Syntetics, lne., as well as the Protease A enzyme described in EP 130 756 A, issued January 9, 1985 and the Protease B enzyme described in EP 303 761 A, issued April 28, 1987 and EP 130 756 A, issued January 9, 1985 See also Bacillus-derived high pH protease sp. NCIMB 40338 described in WO 93/18140 A by Novo. Enzymatic detergents containing a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A by Novo. Other preferred proteases are the protease described in WO 95/10591 A by Proc-

«· · • · * • · · · • · ·«·· · • · ter & Gamble. If necessary, proteases are available which are characterized by reduced adsorption and are more easily hydrolyzed, which are described in WO 95/07791 by Procter & Gamble. A recombinant trypsin-type protease suitable for detergents according to the present invention is described in document WO 94/25583 by Novo.

The protease referred to as Protease D is more precisely a variant of carbonyl hydrolase, containing an amino acid sequence that does not occur in nature, and which is derived from a precursor of carbonyl hydrolase by substituting various amino acids with a series of amino acid residues in positions in the molecule of said carbonyl hydrolase corresponding to the designation +76, preferably also in combination with by one or more amino acid residues at positions corresponding to the labels +99, +101, -103, t!04, +107, +123, +27, +105, +109, +126, +128, +135, -156 , +166, +195, +197, +204, +206, +210, +216, +217, +218, -22, -260, +265, and/or +274 according to the sublysin numbering from Bacillus amyloliquefaciens, described in WO95/10591 and in patent application C. Ghosh, et al., Bleaching Compositions Comprising Protease Enzymes with US Patent Application Serial No. 08/322,677, filed October 13, 1994. Also suitable for use in the methods of this invention are the proteases described in patent applications EP 251 446 and WO91/06637 and the BLAP® protease described in WO91/02792.

Detergents according to this invention, which further contain enzymes capable of breaking down starch, sugars and their derivatives such as amylase, glucoamylase, dextranase, pullulanase, invertase, laccase and insulinase, have been observed to be more effective in removing vegetable and fruit stains and dirt.

The following are documents relating to amylases (α- or β-) which are suitable as components of detergents according to the present invention: Document WO94/02597, Novo Nordisk A/S published 3,

4 ·4 4 44 «· • · · 4 4 4 4 4 4 · 4

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4444 ·*4 44 4 ·4 44 February 1994, describes detergents containing mutant amylases. See also W094/18314, Genencor, published Aug. 18, 1994, W095/10603, Novo Nordisk A/S, published Apr. 20, 1995, and W096/05295, Genencor, published Feb. 22, 1996, Other amylases that are used as components of cleaning preparations are both α-amylase and β-amylase. These α-amylases, which are known according to the prior art, are the amylases described in US Patent No. 5,003,257, EP 252,666, WO/91/00353, FR 2,676,456, EP 285,123, EP 525,610, EP 368 341 and in British Patent Application No. 1 296 839 (Novo). Other suitable amylases are amylases with increased stability, including Purafact Ox Am ^R , described in WO 94/18314, published August 18, 1994, and types of amylases with additional immediate precursor modifications, manufactured by Novo Nordisk A/S, described in WO 95 /10603, published in April 1995, Examples of industrially produced α-amylases are Termamyl®, Ban®, Fungamyl® and Duramyl®, all of which are produced by the Danish company Novo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases. α-amylases with a specific activity measured by the Fadebas amylase activity measurement set at least 25% higher than the specific activity of Termamyl amylase in the temperature range of 25 to 55°C, at a pH in the range of 8 to 10. Other amylolytic enzymes with improved thermostability activity are described in WO95/35382,

Other combinations of saccharolytic enzymes such as β-glucanases (lichenase, laminarase) and exo-glucanases (lignase, tannase, pentosanase, malanase and hemicellulase) with pectolytic enzymes active in an alkaline environment show the advantage of synergistic effects.

Combinations with enzymes that hydrolyze fats and waxes, such as lipases, cutinases, wax esterases and pectolytic enzymes active in an alkaline environment, show a synergistic result* · · ···· ·

·· ·· * » · ·

·*· ··· • · ·· · · ··· • · · ·<· · he effect increased efficiency in removing stains and impurities originating from plant material and fruit.

Suitable lipases for use in detergents are lipases produced by microorganisms of the pseudomonas group, such as the microorganism pseudomonas stutzeri ATCC 19,154, described in British patent 1,372,034. Suitable lipases are lipases that show a positive immunological cross-reaction with antibodies produced by the microorganism pseudomonas fluorescent IAM 1057. Lipase of this type supplied by the Japanese company Amano Pharmaceutical Co. Ltd., Nagoya, under the trade name Lipase P Amano, and is hereinafter referred to as Amano-P. Other suitable commercially available lipases are Amano-CES lipases obtained from chromobacter viscosum, for example from chromobacter viscosum var. lipolyticum NRRLB 3673, supplied by Toyo Jozo Co., Tagata, Japan, lipases obtained from chromobacter viscosum, manufactured by U.S. Biochemical Corp., U.S.A. and the Dutch firm Disoynth Co., and lipases produced by pseudomonas gladioli. Particularly suitable lipases are lipases of the type Ml Lipase®, Lipomax® (Gist-Brocades), Lipolase® and Lipolase Ultra® (Novo), which have been found to be very effective in combination with the preparations of the present invention.

Also suitable are cutinases [EC 3, 1, 1, 50], which can be considered as a special kind of lipases, namely lipases which do not require interfacial activation. The addition of cutinase to detergents is described, for example, in WO-A-88/09367 (Genencor).

Lipases and/or cutinases are usually contained in detergents in concentrations of 0.0001 to 2% by weight of the active enzyme, based on the total weight of the detergents.

The above enzymes may be of any suitable origin, such as plant, animal and bacterial origin, or may be produced by fungi or yeast microorganisms. The mentioned enzymes are usually contained in detergents in concentrations

0.0001 to 2% by weight, based on the weight of the detergent. Enzymes can be added as individual components (granules, stabilized liquids, etc., containing one enzyme), or as mixtures of two or more enzymes (for example, in the form of cogranulates).

The use of other sugars such as β-glucanase (lichenase, laminarase) and exoglucanase (lignase, tannase, pentosanase, malanase and hemicellulase) in combination with pectolytic enzymes active in an alkaline environment has the advantage of a synergistic effect.

Finally, the combination of wax-hydrolyzing enzymes such as lipases, cutinases and wax esterases with pectolytic enzymes active in an alkaline environment brings a synergistic effect that improves the removal of impurities and stains of vegetable and fruit origin. Lipases suitable for use as detergents are lipases produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, by the process described in British Patent 1,372,034. Suitable lipases are also lipases that show a positive immunological cross-reaction with lipase antibodies produced by the Pseudomonas fluorescent IAM 1057. Lipase of this type is manufactured by Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P Amano, and is referred to herein as Amano-P. Other suitable industrially produced lipases are Amano-CES lipases, produced by the microorganism Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB 3673, manufactured by Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum lipases, manufactured by U.S. Biochemical Corp., USA and Disoynth Co., The Netherlands and lipases produced by Pseudomonas gladioli. Particularly suitable lipases are lipases such as Ml Lipase®, Lipomax® (Gist-Brocades), Lipolase® and Lipolase Ultra (Novo), which have been shown to be very effective in combination with the preparations of this invention.

Also suitable are cutinases [EC 3.1.1.50], which can be considered a special kind of lipases, namely lipases that do not require interphase activation. The addition of cutinases to detergent preparations is described, for example, in document WO-A-88/09367 (Genencor).

Lipases and/or cutinases are usually contained in detergents in concentrations of 0.0001 to 2 wt.% of active enzyme, based on the total weight of the detergent.

The above-mentioned enzymes can be of any suitable origin, for example plant, animal, or they can be produced by bacteria, fungi and microorganisms contained in yeast. The mentioned enzymes are usually contained in the detergent in a concentration of 0.0001 to 2 wt.% of the active enzyme, based on the total weight of the detergent. Enzymes can be added as single ingredients (as particles, granules, stabilized liquids, and the like, containing one enzyme), or as mixtures of two or more enzymes (for example, as cogranulates).

Other suitable detergent ingredients that may be added are enzyme oxidation inhibitors, which are described in co-pending European Patent Application No. 92870018.6, filed January 31, 1992. An example of such substances suppressing the oxidation of enzymes are ethoxylated tetraethylene polyamines.

A number of enzymes that are part of synthetic detergents are also described in documents WO 9307263 A and WO 9307260 A, Genencor International, WO 8908694 A, Novo and in the patent

U.S. No. 3,553,139 to McCarty et al., assigned

January 5, 1971. These enzymes are further described in U.S. Patent No. 4,101,457 to Plače et al., issued July 18, 1978, and in U.S. Patent No. 4,507,219 to Hughes, issued

March 26, 1985. Enzymes suitable for liquid detergents and their use in such detergents are described in US Pat.

261,868 to Hora et al., issued Apr. 14, 1981.

Enzymes suitable for use in detergents can be stabilized in various ways. A method of stabilizing enzymes is described and examples of this method are given in US Pat

No. 3,600,319 to Gedge et al., issued August 17, 1991, in EP 199,405 and EP 200,586 to Venegas, issued October 29, 1986. Enzyme system stabilization is also described, for example, in US Pat. 3 519 570. A suitable microorganism, bacillus, sp. AC13, producing proteases, xylanases and cellulases, is described in WO 9401532 A,

New.

Bleaching agents

Furthermore, it has been found that it is possible to achieve the removal of a large number of impurities of plant origin and/or impurities originating from fruit by using detergents containing an enzymatic bleaching system, or a conventional activated bleaching system added to a pectolytic enzyme active in an alkaline environment.

Bleaching agents such as hydrogen peroxide, PBI, PB4 and percarbonate have a particle size of 400-800 micrometers. These bleaching agents may contain one or more oxygenated substances with bleaching effects and, depending on the bleaching agent chosen, one or more bleaching activators. When used, oxygenates with bleaching effects are usually present in concentrations of 1 to 25%.

A bleaching agent suitable for use in the processes according to the present invention can be any bleaching agent suitable for use in cleaning preparations of oxygenated substances with bleaching effects, as well as other substances that are used as bleaching agents. A bleaching agent suitable for use in accordance with the present invention may be an activated or non-activated bleaching agent.

One type of oxygen bleach that can be used are bleaches based on peroxycarboxylic acids and their salts. Suitable examples of these agents are magnesium peroxyphthalate hexahydrate, magnesium salt · ---44-4 44 44 • · · 4 4 4 4 4 4 4 4 · · 4 4 4 4 4 4 · · ·· 444444444 ··· • 4 · · · · ·

4444 ··· 44 4 44 44 ffl-chloroperoxybenzoic acids, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanodioic acid. These bleaching agents are described in US Patent No. 4,483,781, US Patent Application No. 740,446, European Patent Application No. 0,133,354, and US Patent No. 4,412,934. A highly preferred bleaching agent is also 6-nonylamino acid -6oxo-peroxycarbon, described in US Patent No. 4,634,551.

Another type of bleach that can be used are halogen bleaches. Examples of halogen bleaching agents are trichloroisocyanuric acid, sodium and potassium dichloroisocyanurate, N-chloroalkanesulfonamides and N-bromoalkanesulfonamide. These substances are usually added in an amount corresponding to 0.5 to 10 wt.% of the final product, preferably in an amount corresponding to 1 to 5 wt.% of the final product.

Hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US Patent No. 4,412,934), 3,5-trimethylhexanoloxybenzenesulfonate (ISONOBS) described in European Patent No. 120 591, or pentaacetylglucose (PAG) phenolsulfonane ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in document WO 94/28106), the hydrolysis of which produces peroxyacids as active bleaching agents, causing an improved bleaching effect. Suitable activators are acylated citric acid esters, such as those described in co-pending European Patent Application No. 91870207.7.

Suitable bleaching agents, including peroxyacids and bleaching systems containing bleach activators and peroxide bleaches, suitable for use in the detergents of this invention are described in our invention applications • · · · · ·

USSN 08/136 626, PCT/U595/07823, WO95/27772, WO 95/27773,

WO 95/27774 and WO 95/27775.

Hydrogen peroxide may also be added as part of an enzymatic system (i.e., an enzyme and its substrate) capable of generating hydrogen peroxide at the beginning or during washing and/or rinsing. Such enzyme systems are described in European Patent Application No. 91202655.6, filed October 9, 1991.

Peroxidase enzymes are used in combination with oxygen sources such as percarbonate, peroxyborate, peroxysulfate, hydrogen peroxide, and the like. They are used for solution bleaching, i.e. in cases where it is necessary to prevent dyes or pigments from being transferred to other substrates in the same washing solution during washing. Peroxidase enzymes are known from the prior art and are, for example, peroxidase ligninase and halogen peroxidases such as chlorine and bromine peroxidase. Detergents containing peroxidases are described, for example, in International Patent Applications WO 89/099813, WO89/09813, European Patent Application EP No. 91202882.6, filed November 6, 1991, and European Patent Application

No. 96870013.8, filed Feb. 20, 1996. Another oxidase suitable as an ingredient in the detergents of this invention is laccase.

Preferred substances that prevent enzyme oxidation are substituted phenthiazines and phenoxazines, which are 10-phenthiazinepropionic acid (PPT), 10-ethylphenthiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94 /12621) and substituted syringates (C3-C5 alkyl syringates) and phenols. Sodium percarbonate or sodium perborate are preferred sources of hydrogen peroxide.

The mentioned peroxidases are usually contained in detergents in amounts corresponding to a concentration of 0.0001 to 2 wt.% of the active enzyme, based on the total weight of the detergents. Catalyzers metal-containing catalysts for use in bleaching compositions are cobalt-containing catalysts in the form of cobaltite salts, pentamine acetate, and manganese-containing catalysts such as those described in EPA documents 549,271,

EPA 549 72, EPA 458 397, US 5 246 621, EPA 458 398; US 5,194,416 and US 5,114,611. A bleaching agent containing a peroxy compound, a bleaching catalyst with manganese and chelating agents described in the invention application No. 94870206.3.

Bleaching agents other than oxygen bleaching agents are also known and may be used in the processes of this invention. One type of oxygen-free bleaching agent of particular interest is the photoactivated bleaching agent, such as complexes of sulfonated phthalocyanines and zinc or aluminum. These substances are able to be deposited on the substrate during washing, and after irradiation, in the presence of oxygen, which can occur during drying of laundry by hanging in daylight, the sulfonated complex of phthalocyanines and zinc is activated and subsequently bleaching of the substrate occurs. A preferred complex of zinc phthalocyanines and a photoactivated bleaching process are described in US Patent No. 4,033,718. Detergents typically contain 0.025 to 1.25% by weight of a complex of zinc with a sulfonated phthalocyanine.

Inhibition of dye transfer

Improved ability to keep fabrics white and/or enhanced ability to remove dirt have also been observed when the detergents of this invention contain compounds inhibiting the transfer of solubilized and suspended dyes from one fabric to another fabric when washing colored fabrics.

Polymer dye transfer inhibiting agents

Detergents according to the present invention also contain 0.001 to 0.001% by weight, preferably 0.01 to 2% by weight, more preferably 0.05% by weight of polymeric dye transfer inhibiting agent. Said poly• · »· · • · • · · measuring agents inhibiting the transfer of dyes are usually included in cleaning agents in order to inhibit the transfer of dyes from colored fabrics to other fabrics washed together with them. These polymers are capable of complexing or adsorbing dyes that have been washed out of fabrics before these dyes can sorb onto other objects present in the washing solution.

Polyamine N-oxides, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles, or mixtures of these polymeric substances are particularly suitable polymeric dye transfer inhibiting agents. The addition of these polymers also increases the efficiency of the enzymes of this invention.

a) Poly(amine-N-oxides)

Suitable poles (amine-N-oxides) are substances containing structural units of the general formula

P - A _x - R, (I) where P is a polymerizable unit to which the RNO group can be bound, or it is a unit containing this group, or where P is a polymerizable unit fulfilling both of the stated conditions;

0 0

II ll II

A is -NC-, -CO-, -C-, -O-, -S-, -N-; x is 0 or 1;

and R are aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which an N-O group may be attached, or which contain nitrogen in the form of an N-O group.

Said N-0 group has one of the following general formulas:

- 21 • · · · · · o o

II (R 1 ) _x -N-(R 2 ) _y =N-(R 1 ) _Z ,

I (R 3 ) _z wherein R 1 , R 2 , and R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, xa/or ya/or z is 0 or 1, and wherein the nitrogen of the N-0 group may be attached to this groups or form part of them.

This N-0 group may be part of the polymerizable unit (P) or may be attached to the polymer chain, or may be a combination of the two.

Suitable poly(amine-N-oxides) in which the A-0 group forms part of the polymerizable units are poly(amine-N-oxides) in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

One of the mentioned poly(amine-N-oxides) are poly(amine N-oxides) in which the nitrogen of the N-0 group is part of the R group. Preferred poly(amine-N-oxides) are those oxides in which R is heterocyclic a group such as a group derived from pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another group of mentioned poly(amine-N-oxides) is the group of these substances in which the nitrogen of the N-0 group is bound to the R group.

Other suitable pol(amine-N-oxides) are pol(amine-N-oxides) in which the N-O group is attached to a polymerizable unit.

Preferred poly(amine-N-oxides) are poly(amine-N-oxides) of the general formula (I), where R are aromatic, heterocyclic or alicyclic groups, in which the nitrogen of the functional group N-0 is part of said R group.

·· · ·· ♦ ·· ·· ···· · · · · · · ♦ • · · « · · 9 9 9 9

9 9 9 9 9999 9 999 999

9 9 9 9 9 9

9999 999 99 9 99 99

Examples of these types of substances are polyamine oxides in which R is a heterocyclic substance such as pyridine, pyrrole, imidazole and derivatives of these substances.

Another preferred type of poly(amine-N-oxides) are polyamine oxides of general formula (I), where R are aromatic, heterocyclic or alicyclic groups, and where the nitrogen of the functional group N-0 is bound to said R groups.

Examples of polyamine oxides of this kind are polyamine oxides in which the R group may be an aromatic group such as phenyl.

Any main polymer chain can be used as long as the amine oxide polymer obtained is water soluble and has an inhibitory effect on dye transfer. Examples of suitable main polymer chains are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimines, polyacrylic esters and mixtures of these polymers.

The ratio of amines to amine N-oxides in the poly(amine-N-oxides) of this invention is typically 10:1 to 1:1000000. However, the amount of amine oxide groups present in the polyamine oxides can be changed by suitable copolymerization or by a suitable degree of N-oxidation.

Preferably, the ratio of amine to amine N-oxide is 2:3 to 1:1000000, more preferably 1:4 to 1:1000000, most preferably 1:7 to 1:1000000. Specifically used polymers according to the present invention are random polymers or block copolymers in which one monomer is amine-N-oxide and the other monomer can either also be amine-N-oxide or it can be a monomer of another type. The amine oxide structural unit in polyamine N-oxides has a pKa < 10, preferably < 7, more preferably < 6.

The degree of polymerization of the prepared polyamine oxides can be practically arbitrary, provided that the obtained material has the required solubility in water and the ability to suspend dyes, its degree of polymerization is not a decisive property.

• ·

The usual average molecular weight ranges from 500 to 1,000,000; preferably 1,000 to 50,000, more preferably 2,000 to 30,000, most preferably 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone with N-vinylimidazole

The copolymers of N-vinylimidazole with N-vinylpyrrolidone according to the present invention have an average molecular weight in the range of 5,000 to 1,000,000, preferably 5,000 to 200,000.

Highly preferred polymers suitable for use in detergents according to the present invention include a polymer selected from the group consisting of copolymers of N-vinylimidazole and N-vinylpyrrolidone with an average molecular weight of 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

The average molecular weight is determined by the light scattering method described in Barth H.G., Mays J.W. Chemical Analysis Volume 113, Modern Methods of Polymer Characterization.

Highly preferred copolymers of N-vinylimidazole with N-vinylpyrrolidone have an average molecular weight in the range of 5,000 to 50,000; more preferably from 8,000 to 30,000; preferably 10,000 to 20,000.

The molecular weights of N-vinylimidazole copolymers with N-vinylpyrrolidone are in such a range that they are characterized by an excellent ability to inhibit the transfer of dyes and at the same time that the cleaning efficiency of the respective detergents is not adversely affected.

The copolymers of N-vinylimidazole with N-vinylpyrrolidone according to the present invention have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4.

c) Polyvinylpyrrolidone >---·.·· ·· 44 • 4 · · ·--·♦' · · * · • · 4 4 4 4 · 4 · · • 4 · · · »444 4 ··· 444

4 4 4 « 44

4444 444 44 4 44 44

Polyvinylpyrrolidone (PVP) with an average molecular weight is also used in the detergents of the present invention

500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000. Suitable polyvinylpyrrolidones are the following polymers, manufactured by ISP Corporation, New York, NY and Montreal, Canada, under trade names PVP K-15 (viscosity average molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000), and PVP K-90 (average molecular weight 360,000 ). Other suitable polyvinylpyrrolidones available on the market and known to those skilled in the detergent field are the products of BASF Cooperation under the trade names Sokalan HP 165 and Sokalan HP 12; (see for example EP-A-262,897 and EP-A-256,696).

d) Polyvinyl oxazolidone

Polyvinyl oxazolidone can also be used as a polymeric dye transfer inhibitor in the detergents according to the present invention. This polyvinyl oxazolidone has an average molecular weight

500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000.

e) Polyvinylimidazole

Polyvinylimidazole can also be used as a polymeric dye transfer inhibitor in the detergents according to the invention. This polyvinylimidazole has an average molecular weight

500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000.

f) Cross-linked polymers

Cross-linked polymers are polymers whose chains are connected to each other to a certain degree by bonds that are of a chemical or physical nature. On main chains or on branches of these this ·

• toto • · · · · · to • ·· · • to < · · « to · polymers active groups can be bound. Cross-linked polymers are described in Journal of Polymer Science, Vol. 22, p.

1035 to 1039.

In one embodiment, the cross-linked polymers are prepared in such a way that they form a three-dimensional rigid structure in the pores of which dyes can be trapped. In another embodiment, the cross-linked polymers capture the dyes by swelling.

These cross-linked polymers are described in co-pending patent application, 94870213.9.

Detergent ingredients

The cleaning preparations according to the present invention may also contain other components acting as detergents. The specific nature of these other components and their concentration depends on the physical form of the composition and the nature of the cleaning operation used.

The cleaning preparations according to this invention can be liquid, pasty, gel-like, solid in the form of sticks, tablets, powder or granules. Granular preparations can also exist in compact form, liquid preparations can exist in concentrated form.

The composition of the preparations according to the present invention can be chosen, for example, so that they are preparations for washing dishes by hand or preparations for washing dishes in dishwashers, preparations for hand washing and preparations for washing in washing machines, including auxiliary preparations for washing in washing machines, further preparations suitable for soaking and/or pre-washing heavily soiled fabrics, fabric softeners added to steam baths, and products for general household use for cleaning hard surfaces. .

If these preparations are used for washing and if they contain a pectolytic enzyme, the fabric can be cleaned with them, ·♦ « ·

Λ

999 9 ··· *

• · * <· · · a

99999

9 9

9

99 ·> · 9 9

9 9 9

999,999

1

99 bleached, softened, improved its color appearance and at the same time inhibited the transfer of colors from the baths used during washing.

If these preparations are used for manual dishwashing, the preparations according to the present invention preferably contain a surface-active substance and other detergent components, which are organic polymer substances, foaming additives, metal ions II. groups, solvents, hydrotropic agents and additional enzymes.

If these preparations are preparations used for washing in washing machines, they preferably contain both a surface-active substance and a filler, as well as one or more detergent components, which are preferably organic polymer substances, bleaching agents, additional enzymes, antifoam additives, dispersants , additives for dispersing calcium soaps, additives that help disperse impurities and prevent their re-deposition and corrosion inhibitors. Washing products can also contain fabric softeners as additional detergent components.

The preparations according to the present invention can also be used as detergent additives. These additives are intended to extend or improve the effectiveness of conventional detergents.

Detergents according to this invention, used as laundry preparations, can be prepared as needed with a density at 20°C in the range of 400 to 1200 g/l, preferably 600 to 950 g/l.

The degree of compactness of the preparation according to this invention is most clearly manifested in its density, and if it is related to the composition of the preparation, in the content of inorganic salt present as a filler. Inorganic salts used as fillers are common components of detergent in powder form. In common detergents, salts are present in significant amounts, usually 17 to 35% by weight, based on the total weight of the preparation.

In compact compositions, the salt is present in amounts not higher than 15% by weight, preferably 10%, most preferably

5%, based on the total weight of the preparation.

The inorganic salts used as fillers in the preparations according to the present invention are selected from the group consisting of sulfates and chlorides of alkali metals and alkaline earth metals.

The use of sodium sulfate as a filler is preferred.

The liquid detergents according to the invention can also be in a "concentrated form", in which case they contain a lower amount of water compared to conventional liquid detergents.

The usual water content in concentrated liquid detergents is preferably less than 40, more preferably less than 30, most preferably less than 20% by weight, based on the total weight of the product.

Surfactants

The cleaning preparations according to the present invention contain a surfactant system in which these surfactants can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semipolar surfactants. The surfactant is usually contained in concentrations of 0.1% to 60% by weight. More preferred is a content of 1 to 35% by weight, most advantageous is a content of 1% to 30% by weight in the cleaning agent according to the present invention.

Advantageously, surfactants compatible with the enzyme component present in the preparation are used. In a liquid or gel-like preparation, the presence of such a surface-active substance is chosen, which in the most favorable case increases the stability of the enzyme in such a preparation, or at least in such a preparation does not reduce the stability of any enzyme contained therein.

Preferred surfactant systems in the preparations according to the present invention contain as a surfactant one or more of the nonionic and/or anionic surfactants mentioned in this document.

Polyethylene oxide, polypropylene oxide and polybutylene oxide condensates are suitable as nonionic surfactants for use in the processes according to the present invention, and polyethylene oxide condensates are also preferred. These substances are condensation products of alkylphenols with one branched or unbranched alkyl group with 6 to 14 carbon atoms, preferably with 8 to 14 carbon atoms. In a preferred embodiment, ethylene oxide is present in an amount corresponding to 2 to 25 moles, more preferably 3 to 15 moles of ethylene oxide per one mole of alkylphenols. Commercially available nonionic surfactants of this type are Igepal™ CO-630, manufactured by GAF Corporation; and Triton™ X-45, X-114, X-100 and X-102, manufactured by Rohm & Haas Company. These surfactants are usually called alkylphenol alkoxylates (for example, alkylphenol ethoxylates).

Condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for use as nonionic surfactants of nonionic surfactant systems according to the present invention. The alkyl chain of an aliphatic alcohol can be straight or branched, primary or secondary and is usually made up of 8 to 22 carbon atoms. Condensation products of alcohols with one alkyl group containing 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms with 2 to 10 ethylene oxide units per mole of alcohol are preferred. In these condensation products, 2 to 7 moles of ethylene oxide are present, most preferably 2 to 5 moles of ethylene oxide per one mole of alcohol. Examples of industrially produced nonionic surfactants of this type are Tergitol™ 15-S-9 (condensation product of C1 to C15 linear alcohols with 9 moles of ethylene oxide), Tergitol™ 24-L-6 NMW (condensation product of C12 to C14 primary alcohols with 6 moles ethylene oxide with a narrow molecular weight distribution), both of which are manufactured by Union Carbide Corporation, Neodol™ 45-9 (a condensation product of linear alcohols · ·

- 29 moles of C14 to C15 with 9 moles of ethylene oxide), Neodol™ 23-3 (condensation product of linear alcohols C12 to C13 with 3.0 moles of ethylene oxide), Neodol™ 45-7 (condensation product of linear alcohols C14-C15 with 7 moles of ethylene oxide ), Neodol™ 45-5 (condensation product of C14 to C15 linear alcohols with 5 moles of ethylene oxide), manufactured by Shell Chemical Company, Kyro™ EOB (condensation product of C13 to C15 linear alcohols with 9 moles of ethylene oxide), manufactured by Procter & Gamble Company, and Genapol LA 030 or 050 (condensation product of C12 to C14 alcohols with 3 or 5 moles of ethylene oxide) manufactured by Hoechst. The preferred range of HLB values for these products is 8 to 12, the most preferred range of HLB values is 8-10.

Alkyl polysaccharides described in US Patent No. 4,565,647 to Llenado, issued January 21, 1986, which contain a hydrophobic group of 6 to 30 carbon atoms, preferably 10 to 16, are also suitable as nonionic surfactants of the surfactant systems of the present invention. carbon and polysaccharide, for example polyglycoside, hydrophilic group containing 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 carbohydrate units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example glucose, galactose, and glucosyl groups can be substituted with galactosyl groups (a hydrophobic group can be attached at the 2-, 3-, 4-, etc. position, resulting in glucose or galactose as opposed to glucoside or galactoside). Intersaccharide bonds may, for example, be located between one of the positions of the following saccharide units and the 2-, 3-, 4-, and/or 6-positions of the preceding saccharide units.

Preferred alkyl polyglycosides have the formula

R ² 0 (C _n H _2n O) t (glycosyl) _x where R ² is selected from the group of functional groups consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures of these groups in which the alkyl groups contain .10 to 18, with preferably 12 to 14, carbon atoms, n is 2 or 3, preferably 2; t is 0 to 10, preferably 0, and x is 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7. The glycosyl is preferably derived from glucose. In the preparation of these substances, an alcohol or an alkylpolyethoxyalcohol is first prepared and then this substance is reacted with glucose, or a source of glucose, to form a glucoside (bond in position 1). Further glycosyl units can then be attached by linkages between their 1-position and the 2-, 3-, 4- and/or 6- positions of the preceding glycosyl units, preferably predominantly by linkage at the 2-position.

Condensation products of ethylene oxide with a hydrophobic base obtained by condensation of propylene oxide with propylene glycol are also suitable as additional surfactant systems according to the present invention. The hydrophobic part of these substances preferably has a molecular weight of 1500 to 1800 and causes insolubility in water. The attachment of polyoxyethylene units to this hydrophobic part causes an increase in the solubility of this molecule as a whole in water, and the liquid character of this product is maintained up to a total content of polyoxyethylene in the condensation product of about 50% by weight, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of compounds of this type are the surfactants Plurafac™ LF404 and Pluronic™, manufactured by BASF.

Condensation products of ethylene oxide with products resulting from the reaction of propylene oxide with ethylenediamine are also suitable as nonionic surfactants of the systems of nonionic surfactants according to the present invention. The hydrophobic groups in these products are formed by the reaction of ethylenediamine with an excess of propylene oxide, and their molecular weight is usually 2500 to 3000. The condensation reaction of these hydrophobic groups with ethylene oxide proceeds to the extent that the condensation product

·· · · contains 40 to 80% by weight of polyoxyethylene structural units and has a molecular weight of 5,000 to 11,000. Examples of this type of nonionic surfactants are some substances commercially available under the name Tetronic™, which are manufactured by BASF.

Condensation products of polyethylene oxide with alkylphenols, condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide, alkyl polysaccharides, and mixtures of these substances are suitable for use as nonionic surfactants in the surfactant systems of the present invention. Most preferred are C ₈ -Ci ₄ alkylphenol ethoxylates with 3 to 15 ethoxy groups, alcohol ethoxylates derived from C ₈ -Ci 8 alcohols (preferably C 10 ) with 2 to 10 ethoxy groups, and mixtures of these substances.

Highly preferred nonionic surface-active substances are polyhydroxy derivatives of fatty acid amides of the general formula pf-CO-Niť-Z where R ¹ is H or a hydrocarbon residue Ci_4, 2-hydroxyethyl, 2-hydroxypropyl or a mixture of these substances, R ² is a hydrocarbon residue C5_3i and Z is a polyhydroxy derivative of a hydrocarbon residue with an unbranched hydrocarbon chain with at least 3 hydroxyls directly attached to the chain, or an alkylated derivative thereof. R ¹ is preferably methyl, R ² is unbranched C _n - ₁₅ alkyl or C 16-18 alkyl or an alkenyl chain, such as a chain derived from the hydrocarbon residues of the higher fatty acids of coconut oil, or a mixture thereof, and Z is a group derived from a reducing sugar such as glucose, fructose, maltose or lactose by a reductive amination reaction.

Suitable anionic surfactants are unbranched alkylbenzene sulfonate and alkyl ester sulfonate surfactants. · · · · ···· « ··· ··· • · · · · 9.9

9 9 999 99 9 9 9 9 9 breeding actives including unbranched esters of Cs-20 carboxylic acids (ie fatty acids) that are sulfonated with SO ₃ gas by the method described in The Journal of American Oil Chemists Society, Volume 52, p. 323 to 329 (1975), Suitable starting materials are fatty substances of natural origin derived from tallow, palm oil and the like.

A preferred surfactant based on alkyl ester sulfonates, which is particularly suitable as a detergent component of laundry powders, is an alkyl ester sulfonate surfactant of the general formula

R ³ -CH(SO ₃ M) -CO-OR ⁴ where R ³ is a C8-20 hydrocarbon residue, preferably alkyl, or a combination of various of these hydrocarbon residues, R ⁴ is a Ci_6 hydrocarbon residue, preferably alkyl, or a combination of these hydrocarbon residues , and M is a cation, giving water-soluble salts with alkyl ester sulfonates. Cations suitable for salt formation are metal cations such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations based on monoethanolamine, diethanolamine, and triethanolamine. R ³ is preferably C 10-16 alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R ³ is C 3.0-16 alkyl.

Other suitable anionic surfactants are surfactants based on alkyl sulfates, which are water-soluble salts or acids of the general formula ROSO3M, where R is preferably a hydrocarbon residue C ₁₀ -C ₂ 4, preferably alkyl or hydroxyalkyl with an alkyl component Cio~C ₂ o, more preferably alkyl or hydroxyalkyl Ci ₂ -Cia, and M is H or a cation, for example, an alkali metal cation (sodium, potassium, lithium), optionally an ammonium cation or a substituted ammonium cation (for example, a methyl-, dimethyl- or trimethylammonium cation and a quaternary ammonium ·· ·· ø · · 1 ø · · <

cation such as tetramethylammonium or dimethylpiperdinium cation, or quaternary ammonium cation based on alkylamines such as ethylamine, diethylamine, triethylamine, mixtures of these substances and the like). Usually, alkyl chains Gi ₂ -C ₁₆ are preferred for lower washing temperatures (for example below 50 ^° C) and alkyl chains Ci 6 -C 18 are preferred for higher washing temperatures (for example above 50°C).

The cleaning preparations according to the present invention may also contain other anionic surfactants suitable for use as components of detergents. They can be salts (including sodium, potassium, ammonium, and substituted ammonium salts, the cations of which are derived from mono-, di-, and triethanolamine), forming soaps, primary or secondary alkanesulfonates C ₈ -C ₂₂ , olefin sulfonates C ₈ -C ₂ 4, sulfonated polycarboxylic acids prepared by sulfonation of pyrolytic products of alkaline earth metal citrates, which are for example described in British patent No. 1,082,179, Alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide), alkyl glyceryl sulfonates, acyl glyceryl sulfonates with acyls derived from higher fatty acids, oleyl glyceryl sulfate, alkylphenol ethylene oxide - ether sulfates, alkyl sulfonates with higher alkyls, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated monoesters C ₁₂ -C ₂₂ ) and diesters of sulfosuccinates (especially saturated and unsaturated diesters C ₁₂ -C ₁₈ ), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglucosides (non-ionic non-sulfate substances described below), branched primary alkyl sulfates, and alkyl polyethoxycarboxylates of, for example, the general formula

RO (CH 2 CH 2 O) k~CH ₂ COO-M ⁺ ' where R is alkyl C ₈ -C ₂ 2z k is a natural number from 1 to 10 and M is a cation forming a soluble salt. Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and resin ·»ν ·» ·· • » · · · · ♦'··-' · · · · • · ··· · ··· ·· · • · · · • · · · · · · acids and hydrogenated resin acids, present in tallow oil or obtained from tallow oil.

Additional examples are described in Surface Active Agents and Detergents (Vols. I and II, by Schwartz, Perry and Berch).

A number of such surfactants are also described in US Patent No. 3,929,678, issued December 30, 1975, to Laughlin et al., column 23, line 58 through column 9, line 23 (incorporated herein by reference).

If anionic surfactants are used in the detergents according to the invention used as detergents, their content is usually 1 to 40% by weight, preferably 3% to 20% by weight.

Highly preferred anionic surfactants are alkylated sulfates in the form of water-soluble salts or acids of the general formula RO(A) _m SO3M, where R is unsubstituted alkyl Ci ₀ -C ₂ 4 or hydroxyalkyl with alkyl C ₁₀ -C 24 , preferably alkyl or hydroxyalkyl C 12 -C20, more preferably C12-C18 alkyl or hydroxyalkyl, A is ethoxy or propoxy, m is a number greater than zero, usually 0.5 to 6, more preferably 0.5 to 3, and M is H or a cation which may be, for example , a metal cation (ie, for example, a cation of sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium cation or a substituted ammonium cation.

Included in these substances are ethoxylated as well as propoxylated sulfates. Examples of substituted ammonium cations are methylammonium, dimethylammonium, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperdinium cations and cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Examples of surfactants are Ci ₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₈ E (1.0)M), Ci ₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate (Ci ₂ -Ci ₈ E (2.25) Μ), Ci ₂ -Ci ₈ alkyl polyethoxylate (3.0) sulfate (Ci 2 -Ci ₈ E(3.0)M), and Ci ₂ -Ci ₈

• ·

• · · ·· Fr

• fr · · · · • · alkylpolyethoxylate(4,0)sulfate (Ci ₂ -Ci ₈ E (4,0) Μ) , where M is usually sodium or potassium.

The cleaning compositions of this invention may also contain other cationic, ampholytic, zwitterionic, and semipolar surfactants as well as nonionic and/or anionic surfactants than those described herein.

Cationic surfactants with detergent effects, suitable for use in cleaning preparations according to the present invention, are those substances with one hydrocarbon group with a long chain. Examples of such cationic surfactants are ammonium surfactants such as alkyltrimethylammonium halides, and surfactants with the general formula [R ² (OR ³ ) y] [R ⁴ (OR ³ ) y] ₂ R ⁵ N ⁺ X where R ² is an alkyl or benzyl group with 8 to 18 carbon atoms in the alkyl chain, R ³ is one of the groups -CH2CH2-, CH2CH(CH3)-, -CH2CH(CH2OH)-CH2CH2CH2- or a mixture thereof, R ⁴ is one group selected from C1 -C ₄ -alkyls, Ci-C ₄ -hydroxyalkyls, benzyl cyclic structures formed by joining the mentioned two R ⁴ -groups, -CH ₂ GHOH-,-CHOHCOR ₆ CHOHCH ₂ OH, where R ₆ is hexose or polyhexose with a molecular weight lower than 1000, and hydrogen, if y is not 0, R ⁵ is identical to R ⁴ or is formed by an alkyl chain with such a total number of carbon atoms that the sum of the number of carbon atoms in R ² and in R ⁵ is not higher than 18, the values of y vary in the range of 0 to 10, wherein the sum of the values of both y coefficients is 0 to 15, and X is any compatible anion.

Quaternary ammonium surfactants suitable for use in the processes of this invention have the general formula (I):

'4 44 4

4 · 4 ·

4 · · 4 «44 4 4444

4 · .4

444 44 4 • ·

4 4 4 4 4

(I) where R 1 is alkyl with a short chain length (C 6 to C 10 ) or alkylamidoalkyl of general formula (II)

Q is preferably 3, R ² is H or alkyl C1-C3, x is up to 2, most preferably 0, R ³ , R ⁴ and R ⁵ are either alkyls with a short chain length (Cl to C3) alkyls of general formula III where y is 2 to 4, s to 4, preferably 0 the same or different or alkylated

Re

O

(III) where Rg is Ci-C ₄ and 1 or 2, and where X~ is a counterion, preferably a halide, for example chloride or methyl sulfate.

Preferred surfactants based on quaternary ammonium salts are these surfactants of general formula I, in which R ¹ is C ₈ , C _i0 or their mixtures, x = 0,

R ₃ , R ₄ = CH ₃ and C ₅ is CH ₂ CH ₂ OH.

Highly preferred cationic surfactants are quaternary ammonium salts, suitable for use in the preparations according to the present invention, of the general formula:

RiR ₂ R ₃ R ₄ N ⁺ X- (i) where Ri is alkyl C ₈ -Ci _{6 <} R ₂ , R ₃ and R ₄ are independently of each other alkyls Ci-C ₄ hydroxyalkyls Ci~C ₄ , benzyl, and - (C ₂ H ₄ O) _X H, where the value of x is 2 to 5, and X is an anion. Only one of the groups R ₂ , R ₃ and R ₄ can • · · ·

- 37 ·· · · · ·· -99 to be benzyl. The preferred length of the alkyl chain in Ri is Ci ₂ -Ci ₅ especially in cases where it is a mixture of alkyls of different lengths, derived from the fatty acids of coconut oil or palm kernel oil or obtained synthetically from olefins or from alcohols produced by oxosynthesis. The preferred groups R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups, the anion X can be a halide anion, a methyl sulphate anion, an acetate anion and a phosphate anion.

Examples of suitable quaternary ammonium compounds of general formula (i) for use in the processes according to the present invention are:

alkyltriethylammonium chloride or bromide with an alkyl derived from coconut oil fatty acids; alkylmethyldihydroxyethylammonium chloride or bromide; decyltriethylammonium chloride;

decyldimethylhydroxyethylammonium chloride or bromide; alkyldimethylhydroxyethylammonium chloride or bromide with alkyls derived from coconut oil fatty acids; alkyldimethylhydroxyethylammonium chloride or bromide with alkyls derived from coconut oil fatty acids; myristyl trimethylammonium methyl sulfate;

lauryldimethylbenzylammonium chloride or bromide; lauryldimethyl(ethenoxy) ₄ ammonium chloride or bromide; cholinesters (compounds of general formula (i) where R1 is CH2-CH2-O-CO-C12-14 and R2R3R4 are methyls).

dialkylimidazolines [compounds of formula (i)].

Other cationic surfactants of this invention are described in US Patent 4,228,044 to Cambre, issued October 14, 1980 and in European Patent Application EP 000,224.

Typical cationic fabric softeners are fabric softener actives based on quaternary ammonium compounds, which are usually quaternary φ

• φφφ • Φ ·· φ φ · φ • φ φ φ φ φφφ φφφ φ φ φ φ φ φ φ φ φ φ « φ φφφφ ammonium chlorides or methyl sulfates with two alkyl chains.

Preferred cationic fabric softeners of this type are:

1) dialkyldimethylammonium chloride with alkyls derived from beef tallow fatty acids (ditallow dimethylammonium chloride - DTDMAC);

2) hydrogenated dialkyldimethylammonium chloride with alkyls derived from beef tallow fatty acids;

3) hydrogenated dialkyldimethylammonium methylsulfate with alkyls derived from beef tallow fatty acids;

4) distearyldimethylammonium chloride;

5) dioleyldimethylammonium chloride;

6) dipalmitylhydroxyethylmethylammonium chloride;

7) stearylbenzyldimethylammonium chloride;

8) alkyltrimethylammonium chloride with alkyls derived from beef tallow fatty acids;

9) hydrogenated alkyltrimethylammonium chloride with alkyls derived from beef tallow fatty acids;

10) C12-14 alkylhydroxyethyldimethylammonium chloride;

11) C12-18 alkyldihydroxyethylmethylammonium chloride;

12) di(stearoyloxyethyl)dimethylammonium chloride (DSOEDMAC)

13) di(acyloxyethyl)dimethylammonium chloride with alkyls derived from beef tallow fatty acids;

14) dialkylimidazolinium methylsulfate with alkyls derived from beef tallow fatty acids;

15) 1-(2-Alkylamidoethyl)-2-alkylimidazolinium methyl sulfate Biodegradable quaternary ammonium compounds have been proposed as alternatives to the commonly used alkyl aluminum chlorides and methyl sulfates with two long chains. These quaternary ammonium compounds contain long-chain alk(en)yl groups, punctuated by functional groups such as carboxyl groups. Said materials and means for softening39 * ' ·♦

4- 4 9 4 · ·

4 »

4 · · * • » · « «««φ »·· 4 4

44 44 • · 4 9 ·

4 · · · *

4444 4 494 994 . · ·

44 <4 Fabrics containing them are described in a number of documents such as EP-A-0 040 562, and EP-A-0 239 910.

Quaternary ammonium compounds and amine precursors useful in the processes according to the present invention have the following formulas (I) or (II):

^R \ ^{R 2 +} N-(CW Ri

(AND).

R3 R3 + N—(CH ₂ ) _n -CH -CH ₂ Á3 6 ó

II Ti T2 (II) where Q is selected from -Oc(O)- -C (O)-O-, -OC(O)-O-, -NR ⁴ -C(O)-, -C (O) -NR ⁴ -;

R ¹ is (CH ² ) _n -QT ² or T ^{3 ;}

R ² is (CH ₂ ) _m -QT ⁴ or T ⁵ or R ³ ;

R ³ is C 1 -C _{4 alkyl or hydroxyalkyl;}

Τ ¹ , Τ ² , Τ ³ , Τ ⁴ , T ⁵ are independently of each other alkyl or hydroxyalkyl CH-C 22 ;

n and m are natural numbers 1 to 4; and

X is an anion compatible with the fabric softener. Examples of anions compatible with the plasticizer are chloride or methyl sulfate.

Alkyl or alkenyl chains Τ ¹ , Τ ² , Τ ³ , Τ ⁴ , T ⁵ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. Strings can be unbranched or branched.

Beef tallow is a convenient and inexpensive source of compounds containing long alkyls and alkenyls. Particularly preferred are compounds in which Τ ¹ , Τ ² , Τ ³ , T ⁴ and T ⁵ are a mixture of substances usually found in beef tallow and containing long chains.

Examples of quaternary ammonium compounds suitable for use • this·· this ·'· ♦·'· · ·· ·· ·· · this · this • this this · this · this · ·· · ·· that in aqueous fabric softening compositions suitable for use in the processes of this invention are:

1) N,N-di(acyl-oxy-ethyl)-N,N-dimethylammonium chloride with acyls derived from beef tallow fatty acids

2) N,N-di(acyl-oxy-ethyl)-N-methyl-N-(2-hydroxyethyl)ammonium methyl sulfate acyls derived from beef tallow fatty acids

3) N,N-di(2-acyl-oxy-2-oxo-ethyl)-N,N-dimethylammonium chloride with acyls derived from beef tallow fatty acids

4) N,N-di(2-acyl-oxyethyl-carbonyloxyethyl)-N,N-dimethylammonium chloride with acyls derived from beef tallow fatty acids.

5) N-(2-acyl-oxy-2-ethyl)-N-(2-acyloxy-2-oxo-ethyl)-,N,N-dimethylammonium chloride with acyls derived from beef tallow fatty acids;

6) Ν,N,N-tri(acyl-oxy-ethyl)-methylammonium chloride with acyls derived from beef tallow fatty acids

7) N-(2-acyl-oxy-2-oxo-ethyl)-N-(acyl-N,N-dimethylammonium chloride with acyls derived from beef tallow fatty acids; and

8) 1,2-diacyl-oxyethyl-3-trimethylammoniopropane chloride with acyls derived from beef tallow fatty acids; ; and mixtures of said substances.

If these cationic surfactants are present, they are usually contained in the cleaning preparations according to the present invention in amounts of 2% to 25% by weight, preferably 1 to 8% by weight.

Ampholytic surfactants are also suitable for use in the cleaning preparations according to the present invention. These surfactants are generally aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic chain may be unbranched or branched. fcfcfc • fcfc fc * fcfc · fcfc «· • fcfc branched. One of the aliphatic substituents contains at least 8 carbon atoms, usually 8 to 18 carbon atoms, and at least one contains a group promoting water solubility, for example, a carboxy group, a sulfo group, or a sulfate group. Examples of ampholytic surfactants are disclosed in US Patent No. 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18-35.

If these ampholytic surfactants are present, they are usually contained in the cleaning preparations according to the invention in amounts of 0.2% to 15% by weight, preferably 1 to 10% by weight.

Zwitterionic surfactants are also suitable for use in the cleaning preparations according to this invention.

These surfactants are generally derivatives of secondary or tertiary amines, or derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants are disclosed in U.S. Patent No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975, column 19, line 38 through column 22 line 48.

If these zwitterionic surfactants are present, they are usually contained in the cleaning preparations according to the present invention in amounts of 0.2% to 15% by weight, preferably 1 to 10% by weight.

A special type of surfactants are semipolar surfactants, which are water-soluble amine oxides, containing one alkyl of 10 to 18 carbon atoms and 2 groups selected from alkyl and hydroxyalkyl groups, which are alkyl and hydroxyalkyl groups containing 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl of 10 to 18 carbon atoms and 2 groups which are alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms. Semipolar surfactants are also water-soluble • 9 9 «« ·· • 9 9 9 9 9 9

9 9 9 9 9 9 9 • ····♦· 99 9 · · · • · · 9 9 · «9 99 sulfoxides, containing one alkyl with 10 to 18 carbon atoms and an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms .

Semipolar nonionic surfactants are amine oxides with the general formula:

R ³ (OR ⁴ ) X-NO-(R ⁵ ) 2 where R ³ is an alkyl, hydroxyalkyl, or alkylphenyl group or mixtures of these groups containing 8 to 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures of these groups; x is 0 to 3; and R ⁵ is an alkyl or hydroxyalkyl group containing 1 to 3 carbon atoms or a polyethylene oxide group containing 1 to 3 ethylene oxide groups. The R ⁵ groups may be linked to each other, for example by an oxygen atom or a nitrogen atom, to form a ring.

These amine oxide surfactants are particularly alkyldimethylamine oxides with C _{1 8} alkyl and alkoxyethyldihydroxyethyl amine oxides with C ₈ -C _{1 2} alkoxy.

If these semipolar nonionic surfactants are present, they are usually contained in the cleaning preparations according to the present invention in amounts of 0.2% to 15% by weight, preferably 1 to 10% by weight.

The cleaning preparations according to the present invention may further contain another surfactant, selected from the group of primary or tertiary amines.

Suitable primary amines for use in the processes according to the present invention are amines of the general formula RiNH ₂ , where R _x is an alkyl chain C6~C ₁₂ , preferably C ₆ -C ₁₀ , or the group R ₄ X(CH ₂ ) _n , X is - 0-C(O)NH- or -NH-, R ₄ is an alkyl chain C ₆ -Ci ₂ , n is a natural number from 1 to 5, preferably 3. The alkyl chain R 1 can be unbranched or branched and can be interrupted up to 12 , but preferably less than 5, by ethylene oxide structural units.

9 99 9 ·· 99

9999 9·· 9 9··

9 99*9 9999

9999 9999 9 999 999

9 9 9 9 9 9

9999 999 99 9 99 99

Preferred amines of the aforementioned general formula are n-alkylamines. Amines suitable for use in the processes of this invention may be selected from 1-hexylamine, 1-octylamine,

of 1-decylamine and laurylamine. Other preferred primary amines are C ₈ -C ₁₀ oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine.

Suitable tertiary amines for use in the processes of this invention are tertiary amines of the general formula RiR ₂ R ₃ , where Ri and R ₂ are C 1 -C ₈ alkyl or

- (CH ₂ -CHR ₅ -O) _x H, where R ₃ is alkyl Cg-Ci ₂ , preferably alkyl Cg-Cio, or a group

R ₄ X(CH ₂ )n, where X is -0-, -C(0)NH- or -NH-, R ₄ is alkyl C ₄ -C ₁₂ , n is a natural number from 1 to 5, preferably from 2 to 3, R ₅ is H or C 1 -C ₂ alkyl, and the value of x is 1 to 6.

The alkyls R 3 and R ₄ may be unbranched or branched and their chains may be interrupted by up to 12, but preferably less than 5, ethylene oxide structural units.

Preferred tertiary amines are amines of the formula R1R2R3N, where Ri is a C ₆ -Ci ₂ alkyl chain, R ₂ and R ₃ are C 1 -C 3 alkyls or a group of the formula

-(CH ₂ -CHR ₅ -O) _x H, where R ₅ is H or CH ₃ and x = 1-2.

Amidoamines of the general formula are also preferred:

Ri-CO-NH-(CH ₂ ) _and -N-(R ₂ ) ₂ , where Ri is alkyl C6~C ₁₂ , and is a natural number from 2 to 4, preferably 3, R ₂ and R ₃ are C1-C4 .

• 4 • 4 • ♦« • 4 44 » 4 4 4 > 4 4 4

444 444

The most preferred amines of this invention are 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C ₈ -io oxypropylamine, N-alkyl-1,3-diaminopropane with alkyls derived from coconut oil fatty acids, alkyldimethylamine with alkyls derived from fatty acids of coconut oil, lauryldimethylamine, lauryl-bis-(hydroxyethyl)amine, alkylbis(hydroxyethyl)amine with alkyls derived from fatty acids of coconut oil, propoxy derivative of laurylamine with two propoxy groups in the molecule, propoxy derivative of octylamine with two propoxy groups in the molecule, laurylamidopropyldimethylamine, C ₈ -io-amidopropyldimethylamine and C 10 -amidopropyldimethylamine. The most preferred amines for use in the preparations according to this invention are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly suitable are α-dodecyldimethylamine, bis-hydroxyethylalkylamine with alkyls derived from coconut oil fatty acids, ethoxylated oleylamine with 7 ethoxy groups in the molecule, laurylamidopropylamine and alkylamidopropylamine with alkyls derived from coconut oil fatty acids.

Additives reducing bleaching effects

Processes can also be used that allow for a reduced bleaching effect. An example of such procedures is the achievement of a reduced bleaching effect using metalocatalysts (metalocatalysts). These metal catalysts are described in European patent application No. 92870181, 2, which is pending at the same time as this patent application.

Filling system

The preparations according to the present invention may further contain a filler system. Any conventional filler system is suitable for use in the processes of this invention, including systems based on aluminosilicates, silicates, polycarboxylates, alkyl derivatives or alkenyl derivatives of succinic acid and fatty acids, • · »« · ·« · · ·· ·« • · · * • » · · • · · ··· • « ·· ·· compounds such as ethylenediaminetetraacetate, diethylenetriaminepentamethyleneacetate, masking metal ions such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Phosphate-based fillers can also be used.

A suitable filler may be an inorganic ion exchanger, usually an inorganic hydrated aluminosilicate material, especially a hydrated synthetic zeolite such as hydrated zeolites A, X, B, HS or MAP.

Another suitable inorganic filler material is a layered silicate, for example SKS-6 (Hoechst). SKS-6 is a crystalline layered sodium silicate (Na ₂ Si ₂ 0 ₅ ).

Suitable polycarboxylates containing one carboxyl group are lactic acid, glycolic acid and their ether derivatives described in Belgian Patent Nos. 831,368,

821 369 and 821 370. Polycarboxylates containing two carboxy groups are water-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, oxalic acid, tartronic acid, fumaric acid, as well as other carboxylates described in published German patent applications No. 2 446 686,

446,687 and in U.S. Patent No. 3,935,257, and the sulfinyl carboxylates described in Belgian Patent No. 840,623. .1,379,241, lactosuccinates described in Dutch Patent Application No. 7205873 and oxypolycarboxylates such as 2-oxa-1,3-propenetricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups are oxydiasuccinates described in British Patent No. 1,261,829, 1,1,2,2ethanetetracarboxylates, 1,1,3,3-propanetetracarboxylates and « · ·· « <

• · « · ««·· *«· «» « • · · • · · · • · · ·«« · • * · ·· 4 ·· *· • · · · • ♦ · · • »«· ···

4

4 4 4

1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents are sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and US Patent No. 3,936,448, sulfonated pyrolyzed citrates described in British Patent No. 1,082,179 and finally polycarboxylates containing phospho substituents described in British Patent No. 1,439 000.

Alicyclic and heterocyclic polycarboxylates are cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienepentacarboxylates, 2,3,4,5-tetrahydrofuran-cis,cis,cis-tetracarboxylates,

2, 5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl polyol derivatives such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates are derivatives of mellitic acid, pyromellitic acid and phthalic acid, described in British Patent No. 1,425,343,

Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxyl groups in the molecule, especially citrates.

Preferred filler systems for use in the processes of this invention are mixtures of water and an insoluble aluminosilicate filler such as zeolite A or layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid. Preferred filler systems for use in liquid detergents of this invention are soaps and polycarboxylates.

A suitable chelating agent for use in detergents according to this invention is ethylenediamine-N,N'-disuccinic acid (EDDS) its salts with alkali metals, its ammonium salt with alkaline earth metals, or its N-substituted ammonium salts, or mixtures of these substances. Preferred EDDS compounds are mixtures of the sodium or magnesium salt of this acid with the free acid. Examples of preferred sodium salts of EDDS are Na ₂ EDDS and Na ₄ EDDS. Examples of preferred magnesium salts of EDDS are MgEDDS ·· · • · ·· • 9 • 9 • ·

99*9 199 • 9 « • * 9 • · · · • 9 · ·<·9 • · · • 9 «

99 • · · · • 9 9 9 • ·«· 9·· • ·

99 and Mg ₂ EDDS. Magnesium salts are most preferred for use in the preparations according to this invention.

One preferred filler system is a mixture of a water-insoluble aluminosilicate filler such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid.

Other filler materials that may be included in the filler system used for granular preparations are inorganic substances such as alkaline salts of carbonates, bicarbonates, silicates, and organic substances such as organic phosphonates, aminopolyalkylenephosphonates and aminopolycarboxylates.

Other suitable water-soluble organic salts are homo- or copolymeric acids or salts thereof, formed by polycarboxylic acids with at least two carboxyl groups separated from each other by no more than two carbon atoms. Polymers of this type are described in GB-A-1,596,756. Examples of such salts are polyacrylates with a molecular weight of 2000 to 5000 and their copolymers with maleic anhydride, whose molecular weight is in the range of 20,000 to 70,000 and especially in the region of around 40 000.

Filler salts are usually contained in detergents in concentrations of 5 to 80% by weight, preferably 10% to 70% by weight and most preferably 30 to 60% by weight, based on the total weight of the detergents.

Defoaming additives

Another additive that can be used is a defoamer, which can be silicones and mixtures of silica with silicones. Common silicones are alkylated polysiloxanes, silica is usually used in finely powdered forms such as airgels, xerogels and hydrophobic forms of various types of silica. These materials can be used • · · · · · in powder form, in which the antifoam additive is preferably contained in a water-soluble or water-dispersible carrier, which essentially does not have the properties of a surface-active substance and into which the detergent cannot penetrate. the antifoam additive can gradually release. Alternatively, the defoamer may be dissolved or dispersed in a liquid carrier and applied by spraying to one or more other components.

A preferred silicone defoamer is described in U.S. Patent No. 3,933,672 to Bartoloto et al. Other particularly suitable defoamers are the self-emulsifying silicone defoamers described in German Patent Application DTOS 2,646,126, published April 28, 1977. An example of such of substances is DC-544, manufactured by Dow Corning, which is a copolymer of siloxane and glycol. Particularly preferred defoaming additives are defoaming additive systems containing a mixture of silicone oils and 2-alkyl alkanols. A suitable 2-alkyl-alkanol is 2-butyl-octanol, which can be purchased under the trade name Isofol 12 R.

These antifoam additive systems are described in co-pending European Patent Application A 92870174.7, filed November 10, 1992.

Particularly preferred silicone defoamers are described in European Patent Application No. 92201649.8. Said compositions may contain a mixture of silicone and silica in combination with a non-porous silica produced by aerosol precipitation, such as Aerosil®.

The defoaming additives described above are usually used in concentrations of 0.001 to 2% by weight, preferably in concentrations of 0.01 to 1% by weight, based on the total weight of the preparation.

Other ingredients

• · · · · ·

Other ingredients such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, dyes, and/or encapsulated or non-encapsulated perfumes may be used in the cleaning compositions.

Particularly suitable encapsulation materials are water-soluble capsules containing a polysaccharide matrix and the polyhydroxy compounds described in GB 1,464,616.

Other suitable water-soluble encapsulation materials are dextrins obtained from non-cross-linked starch, partially esterified with substituted dicarboxylic acids, described in US Patent 3,455,838. These dextrins are preferably prepared from starch derived from waxy corn, waxy sorghum, sago, tapioca, and potato. A suitable example of the mentioned encapsulation materials is N-Lok, produced by the company National Starch. The encapsulating material N-Lok consists of modified corn starch and glucose. Starch is modified by the introduction of monofunctional substituted groups, such as groups resulting from the modification of the anhydride of the octenyl derivative of jutaric acid.

Antifouling and fouling suspending additives suitable for use in the processes of the present invention are cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homopolymers or copolymers of polycarboxylic acids or their salts. Polymers of this type are polyacrylates, copolymers of maleic anhydride with acrylic acid, mentioned earlier as fillers, as well as copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, wherein maleic anhydride constitutes at least 20 mole percent of the copolymer. These materials are usually used in concentrations of 0.5 to 10% by weight, more preferably 0.75 to 8% by weight, at most 1 to 6% by weight, respectively to the total weight of the product.

Preferred optical brighteners are substances of anionic nature. Examples of these substances are the disodium salt of 4,4'-bis-(2diethanolamino-4-anilino-s-triazin-6-yl-amino)stilben-2:2 ¹ disulfonane, the disodium salt of 4,4'-bis-(2- morpholino-4-anilino-striazin-6-yl-amino-stilbene-2:2'disulfonane, disodium salt of 4,4'-bis-(2,4-dianilino-s-triazin-6-yl-amino)stilbene- 2: 2' disulfonane, sodium salt of 4',4-bis-(2,4-dianilino-s-triazin-6-yl-amino)stilbene-2-sulfonane, disodium salt of 4,4'-bis-(2- anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-yl-amino)stilbene-2,2'disulfonane, disodium salt of 4,4'-bis-(4-phenyl-2, 1,3triazol-2-yl)-stilbene-2,2'disulfonane, 4,4'bis(2anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2 . Highly preferred brighteners are the brighteners listed in European Patent Application No. 95201943, 8, which is pending at the same time as this invention application.

Other suitable polymeric materials are polyethylene glycols, especially those with a molecular weight of 1,000 to 10,000, preferably with a molecular weight of 2,000 to 8,000 and most preferably with a molecular weight close to 4,000. These substances are used in concentrations of 0.20 to 5% by weight, more preferably 0.25 to

2.5% by weight. These polymers and the previously mentioned homopolymers or copolymers of polycarboxylate salts are suitable for improving whiteness, reducing the deposition of particulate impurities, improving cleaning efficiency in the removal of soil pollution, proteinaceous substances and oxidizable impurities in the presence of impurities containing transition metals.

Additives facilitating the release of impurities, suitable for use in the preparations according to the present invention, are common copolymers or terpolymers of terephthalic acid with ethylene glycol and/or · 4 4 4 ·· • · · · 4 ·

4 4 4 4 4 4

44444 4444444

4 4 4

4 4 44 44 propylene glycol units in various configurations. Examples of such polymers are described in U.S. Patent Nos. 4,116,885 and 4,711,730 and in European Published Appl.

No. 0 272 033. According to EP-A0 272 033, a particularly preferred polymer has the general formula:

(CH ₃ (PEG) ₄₃ ) ₀ . ₇₅ (ΡΟΗ) o.25 [T-PO) ₂ . ₈ (TPEG) ₀₍₄ ]T(POH) ₀ . ₂₅ ( (PEG) ₄₃ CH ₃ ) ₀ . ₇₅ where PEG is -(OC ₂ H ₄ )O~, PO is (OC ₃ H ₆ O) and T is (pcOC ₆ H ₄ CO).

Also very suitable are modified polyesters such as random copolymers of dimethyl terephthalate, dimethyl sulfoisophtalate, ethylene glycol and l-2-propanediol, with the end groups mainly being the sulfobenzoate group or the monoester group of ethylene glycol and/or propanediol. The aim is to obtain a polymer terminated at both ends with sulfobenzoate groups, primarily most copolymers suitable for use in the processes according to the invention are terminated with sulfobenzoate groups. Some copolymers are not terminated at both ends by these groups, their end groups can be monoesters of ethylene glycol and/or propane-1,2-diol, and therefore they are formed secondarily by molecules of this type.

Selected polyesters, suitable for use in the processes of this invention, contain 46% by weight dimethyl terephthalic acid, 16% by weight. propane-1,2-diol, 10 wt.% ethylene glycol, 13 wt.% dimethylsulfobenzoic acid, and 15 wt.% sulfoisophthalic acid, and have a molecular weight of approximately 3000. These polyesters and their method of preparation are described in detail in EPA 311 342.

It is known from the prior art that free chlorine in tap water significantly deactivates enzymes contained in detergents. The use of a chlorine scavenger such as peroxyborate, ammonium sulfate, sodium sulfite or polyethylenimine in concentrations of 1% by weight, based on the total weight of the preparation, causes an improvement due to the fact that it improves the stability of the pectolytic enzyme during washing. Preparations containing a chlorine-removing agent are described in European patent application 92870018 6 filed on January 31, 1992.

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are suitable for use in the compositions of this invention because they provide an additional increase in effectiveness in removing greasy impurities. These materials are described in WO 91/08281 and in PCT 90/01815 on page 4 et seq. Chemically, these substances are polyacrylates with one ethoxy side chain for every 7 to 8 acrylate units. These side chains have the general formula (CH ₂ CH ₂ O) _ra (CH ₂ ) _n CH ₃ , where m is 2 to 3 and n is 6 to 12. These side chains are ester-linked to the polyacrylate backbone to form a polymer “ridge-like structures. The molecular weight may vary, but is usually in the range of 2,000 to 50,000. These alkylated polycarboxylates may form 0.05 to 10% by weight of the preparation according to the present invention.

Fabric softeners

Agents for softening fabrics can also be contained in the detergents according to the invention used for washing. These agents can be inorganic or organic substances. Examples of inorganic fabric softeners are smectite clays described in GB-A-1 400 898 in USP 5 019 292. Organic fabric softeners are insoluble tertiary amines described in GB-A-1 514 276 and in EP-B-0 011 340, their combinations with quaternary ammonium salts Ci ₂ -Ci ₄ are described in EP-B-0 026 527 and in EP-B-0 026 528. These agents are also dialkylamides with long alkyl chains, described in EP-B- 0 242 919, Other suitable organic additives for fabric softening systems are the high molecular weight polyethylene oxides described in EP-A-0 299 575 and 0 313 146.

Concentrations of smectite clays are normally in the range of 2 to 20% by weight, more preferably 5° to 15% by weight, these materials are added in dry form to the mixture with the other components forming the preparation. Organic fabric softeners such as water-insoluble tertiary amines or amides with two long alkyl chains are used in concentrations of 0.5% to 5% by weight, usually in concentrations of 1 to 3% by weight, while high molecular weight polyethylene oxide and water-soluble cationic materials are added in concentrations of 0.1 to 2 wt%, usually 0.15 to 1.5 wt%. These materials are usually added to the other components of the preparation obtained by spray drying, in some cases it may be more advantageous to add them in the form of a dry powdery mixture or to spray them in the form of a liquid melt on the other solid components of the preparation.

Methods of washing

The preparations according to the present invention can in principle be used for any washing or cleaning procedure, including soaking, pre-washing and rinsing, whereby a special preparation can be used for rinsing.

The method according to this invention, which is further described in more detail, consists in the normal introduction of fabrics into contact with a detergent.

The method according to the invention is preferably carried out during the cleaning process. This cleaning process is preferably carried out at temperatures of 5 to 95°C, especially at temperatures of 10 to 60°C. The pH values of the solution used preferably range from 7 to 11.

The preferred method of dishwashing in a dishwasher is to apply an aqueous liquid in which an effective amount of dishwashing or rinsing agent is dissolved or dispersed to soiled items. Usually, this effective amount of dishwashing detergent is 8-60 g of product dissolved ··· · • · · · · *

or dispersed in 3 to 10 liters of aqueous liquid, used for washing dishes in a dishwasher.

When washing dishes by hand, dishes with food residues are brought into contact with an effective amount of dishwashing detergent, which is usually 0.5 to 20 g (per 25 dishes washed). The preferred methods of manual dishwashing consist of applying a concentrated solution to the surface of the dishes or soaking the dishes in a large volume of a diluted solution of detergents.

Examples of embodiments of the invention

The purpose of the following examples of embodiments of the invention is to provide specific examples of procedures according to the invention, not to limit or otherwise define the subject matter of the invention.

Enzyme concentrations in detergents are expressed based on the weight of the pure enzyme and are related to the total weight of the product. Unless otherwise stated, the contents of detergent components are expressed on the basis of their weight, relative to the total weight of the preparations. The meaning of the abbreviations of the names of individual components is given below:

LAS sodium dodecylbenzenesulfonate

TAS sodium alkyl sulfate with alkyls derived from beef tallow fatty acids

CXAS

25EY

CXYEZ

XYEZS sodium alkyl sulfate with alkyls C _lx -Ci _Y predominantly linear primary alcohol C]2~Cis, condensed with an average of Y moles of ethylene oxide predominantly linear primary alcohol Ci _X -C _1Y , condensed with an average of Z moles of ethylene oxide sodium salt of alkyl sulfate, with alkyls Ci _X -Ci _Y , condensed on average with Z moles of ethylene oxide • · · · · · ·· ··

···· · · · · · · · • · · · · · · · · · c r * · · · · ···· · 999 999 — JJ ~ 99999 99 9999 999 99 9 99 99 QAS R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ = C ₁₂ -Ci 4 soap sodium salt of fatty acids obtained from a mixture of tallow and coconut oil in a ratio of 80:20 nonionic a mixture of C14-C15 alcohols, ethoxylated with an average of 3.8 moles of ethylene oxide or propoxylated with an average of 4.5 moles of propylene oxide, manufactured by BASF GmbH under the name Plurafac LF404 CFAA alkyl-N-methyl-glucamide with alkyls Ci ₂ -Ci ₄ TFAA alkyl-N-methyl-glucamide with C16- _C18 alkyls DEQA di-(alkyl-oxyethyl)-dimethylammonium chloride with alkyls derived from beef tallow fatty acids SDASA a mixture of stearyldimethylamine and stearic acid in a ratio of 1:2 He didn't hold back 45-13 ethoxylated mixture of C14-C15 alcohols, manufactured by Shell Chemical Co. silicate amorphous sodium silicate (ratio SiO ₂ :Na ₂ O = 2.0) NaSKS-6 crystalline layered silicate 8-Na ₂ Si ₂ O ₅ carbonate anhydrous sodium carbonate with a particle size in the range of 200 to 900 pm hydrogen- carbonate anhydrous sodium bicarbonate with a particle size of 400 to 1200 pm STPP anhydrous sodium triphosphate MA/AA copolymer of maleic acid with acrylic acid, molar ratio of monomers 1:4, average molecular weight 80,000 PA30 polyacrylic acid with an average molecular weight of 8,000 terpolymer terpolymer of acrylic acid, maleic acid and ethylacrylic acid, molar ratio of monomers 60:20:20, average molecular weight 7,000

9 99 9 «9 ·· 9 9 9 9 999 9999 9 9 9999 9999 _ C/C _ 9 9 9 9 9 9999 9 999 999 «-J VJ 99999 99 9999 999 99 9 99 99 480N statistical copolymer of acrylic acid with methacrylic acid, molar ratio of monomers 3:7, average molecular weight 3500 polyacrylate polyacrylate with molecular diameter, wt 8,000, manufactured by BASF under the trade name PA30 zeolite Ά hydrated sodium aluminosilicate Nai2 (AI2SÍO2) 12 · 27H ₂ O citrate trisodium citric acid dihydrate with an activity of 86.4% and a molecular weight distribution of 425 to 850 gm lemon anhydrous citric acid PB1 bleaching agent based on sodium peroxyborate monohydrate, empirical formula NaBO2.H ₂ 0 ₂ PB4 sodium peroxyborate tetrahydrate peroxycarbonate bleach based on sodium percarbonate, empirical formula 2Na ₂ CO3.3H ₂ O ₂ TAED tetraacetylethylenediamine NOBS sodium nonanoylbenzenesulfonate photoactivated bleaching agent sulfonated zinc phthalocyanine, encapsulated in a dextrin-soluble polymer PAAC cobalt salt of pentaaminoacetic acid paraffin paraffin oil supplied by Wintershall under the trade name Winog 70 BzP benzoyl peroxide pectolytic enzyme pectin-degrading enzyme produced by the microorganism Bacillus P-4-A, see Agr. Biol. Chem. 36(2), 285-93 (1972). protease proteolytic enzymes supplied under the brand names Savinase, Alcalase, Durazym by the company Novo Nordisk AS, or under the trademarks Maxacal, Maxapem by Gist-Brocades and these enzymes described in patents WO91/06637 and/or WO95/10591 and/or EP 251 446

·· 4 ·· · ·« ·· • · ·· · 9 · · · · ·

9 9 9 9 9 9 9 9 9

9999 9999 9 999 999

9 9 9 9 9 9

9999 999 99 9 99 99

- 57 silicone defoamer granular defoamer

SRP 1

SRP2 sulfate

HMWPEO

PEG

BTA

NaDCC encapsulated perfume

KOH polydimethylsiloxane defoamer with oxyalkylene-siloxane copolymer as dispersant, component ratio 10:1 to 100:1

12% silicone/silica, 18% stearyl alcohol 70% starch, in granular form linear polymers based on a copolymer containing oxyethylene and terephthaloyl structural units, terminated with sulfobenzoyl ester groups diethoxylated poly(1,2-propylene terephthalate) with short blocks anhydrous sodium sulfate high molecular weight polyethylene oxide polyethylene glycol benzotriazole sodium dichloroisocyanurate release method of insoluble perfume using zeolite 13X, perfume and agglomerating binder dextrose/glycerol potassium hydroxide solution, 100% activity pH measured as a 1% solution in water

• · • · ···· · ·· ·* • · · • · » • · · · · · • · ·· ··

Example 1

The following detergents, used as washing preparations, were prepared by the methods of the present invention:

1 II lil IV IN VI LAS (wt%) 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 (wt%) 3.4 3.4 3.4 3.4 3.4 3.4 QAS (wt%) 0.8 0.8 0.8 0.8 zeolite A (wt%) 18.1 18.1 18.1 18.1 18.1 18.1 carbonate (wt%) 13.0 13.0 13.0 27.0 27.0 27.0 silicate (wt%) 1.4 1.4 1.4 3.0 3.0 3.0 sulfate (wt%) 26.1 26.1 26.1 26.1 26.1 26.1 PB4 (wt%) 9.0 9.0 9.0 9.0 9.0 9.0 TAED (wt%) 1.5 1.5 1.5 1.5 1.5 1.5 DETPMP (wt%) 0.25 0.25 0.25 0.25 0.25 0.25 HEDP (wt%) 0.3 0.3 0.3 0.3 0.3 0.3 pectolytic enzyme (wt%) 0.005 0.01 0.05 0.01 0.02 0.08 protease (wt%) 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026 amylase (wt%) 0.0009 0.0009 0.0009 0.0009 0.0009 0.0009 MA/AA (wt%) 0.3 0.3 0.3 0.3 0.3 0.3 CMC (wt%) 0.2 0.2 0.2 0.2 0.2 0.2 photoactivated bleaching agent (ppm) 15 15 15 15 15 15 brightener (wt%) 0.09 0.09 0.09 0.09 0.09 0.09 perfume (wt%) 0.3 0.3 0.3 0.3 0.3 0.3 silicone defoamer (wt%) 0.5 0.5 0.5 0.5 0.5 0.5 other various ingredients up to 100% density (kg/m ³ ) 850 850 850 850 850 850

«4 · • 4

Β 4 • 44 4

4

Example 2

The following granulated detergents with a density of 750 kg/m ³ were produced using the procedures according to this invention:

AND II III LAS (wt%) 5.25 5.61 4.76 TAS (wt%) 1.25 1.86 1.57 C45AS (wt%) 2.24 3.89 C25AE3S (wt%) 0.76 1.18 C45E7(wt%) 3.25 5.0 C25E3 (wt%) 5.5 QAS (wt%) 0.8 2.0 2.0 STPP (wt%) 19.7 zeolite A (wt%) 19.5 19.5 citric acid (wt%) (79:21) 10.6 10.6 carbonate (wt%) 6.1 21.4 21.4 bicarbonate (wt%) 2.0 2.0 silicate (wt%) 6.8 sodium sulfate (wt%) 39.8 14.3 PB4 (wt%) 5.0 12.7 TAED (wt%) 0.5 3.1 DETPMP (wt%) 0.25 0.2 0.2 HEDP (wt%) 0.3 0.3 pectolytic enzyme (wt%) 0.001 0.02 0.0006 protease (wt%) 0.0026 0.008 0.045 lipase (wt%) 0.003 0.003 0.003 cellulase (wt%) 0.0006 0.0006 0.0006 amylase (wt%) 0.0009 0.0009 0.0009 MA/AA (wt%) 0.8 1.6 1.6 CMC (wt%) 0.2 0.4 0.4 photoactivated bleaching agent (ppm) 15 27 27 brightener! agent 1 (wt%) 0.08 0.19 0.19 brightener! agent 2 (wt%) 0.04 0.04 encapsulated perfume (wt%) 0.3 0.3 0.3 silicone defoamer (wt%) 0.5 2.4 2.4

various other ingredients up to 100% » » 4 4 4 4 • 4 ·· 44

Example 3

The processes of this invention prepared the following detergents I to III, where I is a phosphate-containing detergent, II is a zeolite-containing detergent, and III is a compact detergent.

AND II lil powder STPP (wt%) zeolite A (wt%) 24.0 24.0 24.0 C45AS (wt%) 9.0 6.0 13.0 MA/AA (wt%) 2.0 4.0 2.0 LAS (wt%) 6.0 8.0 11.0 TAS (wt%) 2.0 silicate (wt%) 7.0 3.0 3.0 CMC (wt%) 1.0 1.0 0.5 brightener 2 (wt%) 0.2 0.2 0.2 soap (wt%) 1.0 1.0 1.0 DETPMP (wt%) 0.4 0.4 0.2 sprayed ingredients C45E7 (wt%) 2.5 2.5 2.0 C25E3 (wt%) 2.5 2.5 2.0 silicone defoamer (wt%) 0.3 0.3 0.3 perfume (wt%) 0.3 0.3 0.3 dry ingredients carbonate (wt%) 6.0 13.0 15.0 PB4 (wt%) 18.0 18.0 10.0 PB1 (wt%) 4.0 4.0 0 TAED (wt%) 3.0 3.0 1.0 photoactivated bleaching agent (ppm) 0.02 0.02 0.02 pectolytic enzyme (wt%) 0.05 0.05 0.01 protease (wt%) 0.01 0.01 0.01 lipase (wt%) 0.009 0.009 0.009 amylase (wt%) 0.002 0.003 0.001 sodium sulfate 3.0 3.0 5.0 other various ingredients up to 100% density (kg/m ³ ) 630.0 670.0 670.0

- 61 ·· »

··· 9 frfr ·· • 0 · Λ · fr · • · · · · » fr • · · ·*·· « *·· frfrfr • · · · · * *· · ·« ··

Example 4

The processes of the present invention have prepared the following detergents containing no bleaching agent, which are particularly suitable for washing colored garments:

1 II III powder zeolite A (wt%) 15.0 15.0 sodium sulfate (wt%) 0.0 5.0 LAS (wt%) 3.0 3.0 DETPMP (wt%) 0.4 0.5 CMC (wt%) 0.4 0.4 MA/AA (wt%) 4.0 4.0 agglomerates C45AS (wt%) LAS (wt%) 6.0 5.0 11.0 TAS (wt%) 3.0 2.0 silicate (wt.%j 4.0 4.0 zeolite A (wt%) 10.0 15.0 13.0 CMC (wt%) 0.5 MA/AA (wt%) 2.0 carbonate (wt%) 9.0 7.0 7.0 sprayed ingredients perfume (wt%) 0.3 0.3 0.5 C45E7 (wt%) 4.0 4.0 4.0 C25E3 (wt%) 2.0 2.0 2.0 dry ingredients MA/AA (wt%) 3.0 Citrate (wt%) 10.0 8.0 bicarbonate (wt%) 7.0 3.0 5.0 carbonate (wt%) 8.0 5.0 7.0 PVPVI/PVNO (wt%) 0.5 0.5 0.5 pectolytic enzyme (wt%) 0.05 0.005 0.02 protease (wt%) 0.026 0.016 0.047 lipase (wt%) 0.009 0.009 0.009 amylase (wt%) 0.005 0.005 0.005 cellulase (wt%) 0.006 0.006 0.006 silicone defoamer (wt%) 5.0 5.0 5.0 sodium sulfate (wt%) 0.0 9.0 0.0 other various ingredients up to 100% density (kg/m ³ ) 700 700 700

Example 5 • · · · • » · • * · • · · · · · • · • · e ·

The procedures according to this invention were prepared with the following detergents:

1 II III IV LAS (wt%) 20.0 14.0 24.0 22.0 QAS (wt%) 0.7 1.0 0.7 TFAA 1.0 C25E5/C45E7 (wt%) 2.0 0.5 C45E3S (wt%) 2.5 STPP (wt%) 30.0 18.0 30.0 22.0 silicate (mass.%) 9.0 5.0 10.0 8.0 carbonate (wt%) 13.0 7.5 5.0 bicarbonate (wt%) 7.5 DETPMP (wt%) 0.7 1.0 SRP 1 (wt%) 0.3 0.2 0.1 MA/AA (wt%) 2.0 1.5 2.0 1.0 CMC (wt%) 0.8 0.4 0.4 0.2 pectolytic enzyme (wt%) 0.08 0.04 0.05 0.01 protease (wt%) 0.008 0.01 0.026 0.026 amylase (wt%) 0.007 0.004 0.002 lipase (wt%) 0.004 0.002 0.004 0.002 cellulase (wt%) 0.0015 0.0005 photoactivated bleaching agent (ppm) 70 ppm 45 ppm 10 ppm brightener 1 (wt%) 0.2 0.2 0.08 0.2 PB 1 (wt%) 6.0 2.0 NOBS (wt%) 2.0 1.0 other various ingredients up to 100%

Example 6

The procedures according to this invention were prepared with the following detergents:

IV powder

zeolite A (wt%) 30.0 22.0 6.0 6,7 On SkS-6 (wt%) 3.3 polycarboxylate (wt%) 7.1 sodium sulfate (wt%) 19.0 5.0 7.0 MA/AA (wt%) 3.0 3.0 6.0 LAS (wt%) 14.0 12.0 22.0 21.5 C45AS (wt%) 8.0 7.0 7.0 5.5 cationic (wt%) 1.0 silicon (wt%) 1.0 5.0 11.4 soap (wt%) 2.0 brightener! agent 1 (wt%) 0.2 0.2 0.2 carbonate (wt%) 8.0 16.0 20.0 10.0 DETPMP (wt%) 0.4 0.4 sprayed ingredients C45E7 (wt%) 1.0 1.0 1.0 3.2 dry ingredients PVPVI/PVNO (wt%) 0.5 0.5 0.5 pectolytic enzyme (wt%) 0.005 0.01 0.01 0.005 protease (wt%) 0.052 0.01 0.01 0.01 lipase (wt%) 0.009 0.009 0.009 0.009 amylase (wt%) 0.001 0.001 0.001 0.001 cellulase (wt%) 0.0002 0.0002 0.0002 0.0002 NOBS (wt%) 6.1 4.5 3.2 PB 1 (wt%) 1.0 5.0 6.0 3.9 sodium sulfate (wt%) 6.0

other various ingredients up to 100% • * · · · · • · · · · · • · · · · · · ····· · ··· ··· • · · · • · * · ·' ·

Example 7

The following high-density detergents containing a bleaching agent were prepared according to the processes of this invention:

1 II III powder zeolite A (wt%) 15.0 15.0 15.0 sodium sulfate (wt%) 0.0 5.0 0.0 LAS (wt%) 3.0 3.0 3.0 QAS (wt%) 1.5 1.5 DETPMP (wt%) 0.4 0.4 0.4 CMC (wt%) 0.4 0.4 0.4 MA/AA (wt%) 4.0 2.0 2.0 agglomerates LAS (wt%) 5.0 5.0 5.0 TAS (wt%) 2.0 2.0 1.0 silicate (wt%) 3.0 3.0 4.0 zeolite A (wt%) 8.0 8.0 8.0 carbonate (wt%) 8.0 8.0 4.0 sprayed ingredients perfume (wt%) 0.3 0.3 0.3 C45E7 (wt%) 2.0 2.0 2.0 C25E3 (wt%) 2.0 dry ingredients Citrate (wt%) 5.0 2.0 bicarbonate (wt%) 3.0 carbonate (wt%) 8.0 15.0 10.0 TAED (wt%) 6.0 2.0 5.0 PB 1 (wt%) 14.0 7.0 10.0 polyethylene oxide, m.h. 5,000,000 (wt%) 0.2 bentonite (wt%) 10.0 pectolytic enzyme (wt%) 0.005 0.01 0.08 protease (wt%) 0.01 0.01 0.01 lipase (wt%) 0.009 0.009 0.009 amylase (wt%) 0.005 0.005 0.005 cellulase (wt%) 0.002 0.002 0.002 silicone defoamer (wt%) 5.0 5.0 5.0 of sodium (wt%) 0.0 3.0 0.0 other various ingredients up to 100% density (kg/m ³ ) 850 850 850

Example 8 • · 4 ► · · » · · • · · 4 • · 4

The following high density detergents were prepared using the methods of this invention:

II

agglomerates C45AS 11.0 14.0 zeolite A (wt%) 15.0 6.0 carbonate (wt%) 4.0 8.0 MA/AA (wt%) 4.0 2.0 CMC (wt%) 0.5 0.5 DETPMP(wt%) 0.4 0.4 sprayed ingredients C25E5 (wt.% 5.0 5.0 perfume (wt%) 0.5 0.5 dry ingredients HEDP (wt%) 0.5 0.3 SKS 6 (wt%) 13.0 10.0 Citrate (wt%) 3.0 1.0 TAED (wt%) 5.0 7.0 percarbonate (mass.%) 20.0 20.0 SRP 1 (wt%) 0.3 0.3 pectolytic enzyme (wt%) 0.02 0.05 protease (wt%) 0.04 0.04 lipase (wt%) 0.009 0.009 cellulase (wt%) 0.004 0.004 amylase (wt%) 0.005 0.005 silicone defoamer (wt%) 5.0 5.0 brightener 1 (wt%) 0.2 0.2 brightener 2 (wt%) 0.2 other various ingredients up to 100% density (kg/m ³ ) 850 850

· · · · · · ·

Example 9

Procedures according to this granulated detergents: of the invention were prepared further listed AND II III IV IN LAS (wt%) alkyl sulfate ¹ (wt%) 21.0 25.0 18.0 18.0 21.9 AE3S (wt%) 1.5 1.5 2.3 decyldimethylhydroxyethylhydroxyethylammonium chloride (wt%) 0.4 0.7 0.7 0.8 nonionic (wt%) ester ¹ (wt%) 1.2 0.9 0.5 1.0 STPP (wt%) 44.0 25.0 22.5 22.5 22.5 Zeolite A (wt%) MA/AA (wt%) 7.0 10.0 0.9 0.9 8.0 SRP 1 (wt%) 0.3 0.15 0.2 0.1 0.2 CMC (wt%) 0.3 2.0 0.75 0.4 1.0 carbonate (wt%) 17.5 29.3 5.0 13.0 15.0 silicate (mass.%) 2.0 7.6 7.9 pectolytic enzyme (wt%) 0.005 0.01 0.007 0.01 0.01 protease (wt%) 0.007 0.007 0.007 0.007 0.007 amylase (wt%) 0.004 0.004 0.004 0.004 lipase (wt%) 0.003 0.003 0.003 cellulase (wt%) 0.001 0.001 0.001 0.001 NOBS (wt%) 1.2 1.0 PB 1 (wt%) 2.4 1.2 diethylenetriaminepentaacetic acid (wt%) diethylenetriaminepentaacetic acid 0.6 0.7 1.0 magnesium sulfate (wt%) 0.8 photoactivated bleaching agent (ppm) 45 50 15 45 42 brightener 1 (wt%) 0.05 0.04 0.04 0.04 brightener 2 (wt%) 0.1 0.3 0.05 0.13 0.13 water and other various ingredients up to 100%

'alkyl sulfate with alkyls derived from coconut oil fatty acids 'coconut oil fatty acid ester with C12-C14 alcohols

Example 10

The following liquid detergents were prepared according to the procedures of this invention:

AND II III IV V VI VII He poured LAS (wt%) 10.0 13.0 9.0 25.0 C25AS (wt%) 4.0 1.0 2.0 10.0 13.0 18.0 15.0 C25E3S (wt%) 1.0 3.0 2.0 2.0 4.0 C25E7 (wt%) 6.0 8.0 13.0 2.5 4.0 4.0 TFAA (wt%) 4.5 6.0 8.0 8.0 QAS (wt%) 3.0 1.0 TPKFA (wt%) 2.0 13.0 2.0 15.0 7.0 7.0 rapeseed oil fatty acids 5 0 4 0 4 0 (wt%) citric acid (wt%) 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 succinic acid (wt%) 12.0 10.0 15.0 oleic acid (wt%) 4.0 2.0 1.0 1.0 ethanol (wt%) 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 - propanediol (wt%) 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0 monoethanolamine (wt%) 5.0 9.0 9.0 triethanolamine (wt%) 8.0 pH - adjusted with NaOH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 ethoxylated tetraethylenepentamine 0 5 0 5 0 2 04 0.3 (wt%) DETPMP (wt%) 1.0 1.0 0.5 1.0 2.0 1.2 1.0 SRP 2 (wt%) 0.3 0.3 0.1 0.2 0.1 PVNO (wt%) 0.10 pectolytic enzyme (wt%) 0.005 0.005 0.005 0.005 0.05 0.07 0.02 0.01 protease (wt%) 0.005 0.005 0.004 0.003 0.008 0.005 0.003 0.006 lipase (wt%) 0.002 0.001 0.003 0.003 amylase (wt%) 0.002 0.002 0.005 0.004 0.002 0.008 0.005 0.005 cellulase (wt%) 0.001 0.002 0.001 boric acid (wt%) 0.1 0.2 2.0 1.0 1.5 2.5 2.5 sodium formate (wt%) 1.0 calcium chloride (wt%) 0.01 0.01 bentonite (wt%) 4.0 4.0 clay SD3 (wt%) 0.6 0.3

water and other various ingredients up to 100%

- 68 • · · ·

Example 11

The following granulated cleaning preparations were prepared using the procedures according to this invention, which are characterized by the ability to "soften during washing:

II

45AS (wt%) 10.0 LAS (wt%) 7.6 68AS (wt%) 1.3 45E7 (wt%) 4.0 25E3 (wt%) 5.0 quaternary ammonium salt ¹ (wt%) 1.4 1.0 Citrate (wt%) 5.0 3.0 Na-SKS-6 (wt%) 11.0 Zeolite A (wt%) 15.0 15.0 MA/AA (wt%) 4.0 4.0 DETPMP (wt.%) 0.4 0.4 PB1 (wt%) 15.0 percarbonate (wt%) 15.0 TAED (wt%) 5.0 5.0 smectite clay (wt%) 10.0 10.0 HMWPEO (wt%) 0.1 pectolytic enzyme (wt%) 0.01 0.01 protease (wt%) 0.02 0.1 lipase (wt%) 0.02 0.01 amylase (wt%) 0.03 0.005 cellulase (wt%) 0.001 silicate (wt%) 3.0 5.0 carbonate (wt%) 10.0 10.0 granular defoamer (wt%) 1.0 4.0 CMC (wt%) 0.2 0.1

water and other various additives to 100% 'alkyldimethylhydroxyethylammonium chloride with alkyls derived from coconut oil fatty acids • · 4 · • 4 9 9 * * · • 4 9 9*4 *

• » »#

Example 12

The procedures according to this invention were prepared the following Preparations for softening fabrics added to the rinsing bath:

plasticizer active ingredient (wt%) 20.0 pectolytic enzyme (wt%) 0.01 amylase (wt%) 0.001 cellulase (wt%) 0.001 HCI (wt%) 0.03 defoamer (wt%) 0.01 blue dye (ppm) 25 calcium chloride (ppm) (wt%) 0.20 perfume (wt%) 0.90 water and other various ingredients up to 100%

- 70 » ·

Example 13 • · · · • · · * · · 9

9 9 999 ·

• * 9 9

Preparations for softening fabrics were prepared according to the procedures of this invention:

listed below

AND II III DEQA (wt%) 2.6 19.0 SDASA (wt%) 70.0 stearic acid (wt%) 0.3 Neodol 45-13 (wt%) 13.0 hydrochloric acid (wt%) 0.02 0.02 ethyl alcohol (wt%) 1.0 PEG (wt%) 0.6 pectolytic enzyme (wt%) 0.005 0.05 0.01 perfume (wt%) 1.0 1.0 0.75 digeranyl succinate (wt%) 0.38 silicone defoamer (wt%) 0.01 0.01 electrolyte (ppm) 600 dye (ppm) 100 50 0.01

water and other various ingredients up to 100% • · • · · · * · · • · · • · · · · ·

Example 14

The following preparations of the syndet bar type for cleaning fabrics were prepared according to the procedures of this invention:

1 II III IV C26 AS (wt%) 20.00 20.00 20.00 20.00 CFAA (wt%) 5.0 5.0 5.0 5.0 LAS(C11 -13) (wt%) 10.0 10.0 10.0 10.0 sodium carbonate (wt%) 25.0 25.0 25.0 25.0 sodium pyrophosphate (wt%) 7.0 7.0 7.0 7.0 STPP (wt%) 7.0 7.0 7.0 7.0 Zeolite A (wt%) 5.0 5.0 5.0 5.0 CMC (wt%) 0.2 0.2 0.2 0.2 polyacrylate (MW 1400) (wt%) 0.2 0.2 0.2 0.2 alkylmethanolamide ¹ (wt%) 5.0 5.0 5.0 5.0 pectolytic enzyme (wt%) 0.1 0.1 0.15 0.2 amylase (wt%) 0.01 0.02 0.01 0.01 protease (wt%) 0.3 0.5 0.05 brightener, perfume (wt%) 0.2 0.2 0.2 0.2 calcium sulfate (wt%) 1.0 1.0 1.0 1.0 magnesium sulfate (wt%) 1.0 1.0 1.0 1.0 water (wt%) 4.0 4.0 4.0 filler up to 100% 4.0

'alkylmethanolamide with alkyls derived from coconut oil fatty acids

- 72 Example 15

The following high-density dishwashing preparations (960 kg/m ³ ) were prepared using the procedures according to this invention:

1 II III IV IN VI STPP (wt%) 49.0 38.0 Citrate (wt%) 33.0 17.5 54.0 25.4 carbonate (wt%) 17.5 20.0 14.0 25.4 silicate (wt%) 33.0 14.8 20.4 14.8 14.8 metasilicate (wt%) 2.5 2.5 PB1 (wt%) 1.9 9.7 7,8 14.3 7,8 PB4 (wt%) 8.6 percarbonate (mass.%) 6,7 nonionic (wt%) 1.5 2.0 1.5 1.5 1.5 2.6 TAED (wt%) 4.8 2.4 2.4 2.4 4.0 HEDP (wt%) 0.8 1.0 0.5 DETPMP (wt%) 0.6 0.6 PAAC (wt%) 0.2 BzP (wt%) 4.4 paraffin (wt%) 0.5 0.5 0.5 0.5 0.5 0.2 pectolytic enzyme (wt%) 0.07 0.05 0.1 0.1 0.08 0.01 protease (wt%) 0.075 0.05 0.10 0.10 0.08 0.01 lipase (wt%) 0.001 0.005 amylase (wt%) 0.01 0.005 0.015 0.015 0.01 0.0025 BTA (wt%) 0.3 0.3 0.3 0.3 0.3 bismuth nitrate (wt%) 0.3 PA30 (mass.%) 4.0 terpolymer (wt%) 4.0 480N (mass.%) 6.0 2.8 sulfate (mass.%) 7.1 20.8 8.4 0.5 1.0 pH -1% solution 10.8 11.0 10.9 10.8 10.9 9.6

4 • 44 •

4 · 4

4«

4

4

4 4 4 • 4

Example 16

The following granulated dishwashing detergents I to IV with a density of 1020 kg/m ³ were prepared using the procedures according to this invention:

1 II III IV IN VI STPP (wt%) 30.0 30.0 30.0 27.9 34.5 26.7 carbonate (mass.%) 30.5 30.5 30.5 23.0 30.5 2.80 silicate (wt%) 7.4 7.4 7.4 12.0 8.0 20.3 PB1 (wt%) 4.4 4.4 4.4 4.4 NaDCC (mass.%) 2.0 1.5 Nonionic (wt%) 0.75 0.75 0.75 1.9 1.2 0.5 TAED (wt%) 1.0 1.0 1.0 PAAC (wt%) 0.004 BzP (wt%) 1.4 paraffin (wt%) 0.25 0.25 0.25 pectolytic enzyme (wt%) 0.01 0.01 0.01 0.05 0.01 0.05 protease (wt%) 0.05 0.05 0.05 0.1 lipase (wt%) 0.005 0.001 amylase (wt%) 0.003 0.001 0.01 0.02 0.01 0.015 BTA (wt%) 0.15 0.15 sulfate (wt%) 23.9 23.9 23.9 31.4 17.4 pH -1% solution 10.8 10.8 10.8 10.7 10.7 12.3

Example 17 ·♦ * φ· ·· • · · · « · ·

9 9 9 9 9 9 9

999999 999 9 99

9 9 9 9 • · · · · 9 9

The following 25 g detergent tablets were prepared by pressing granulated dishwashing detergent at a pressure of 130 MPa using a conventional twelve-head rotary press:

1 II III STPP (wt%) 48.8 47.5 Citrate (wt%) 26.4 carbonate (wt%) 5.0 silicate (wt%) 26.4 14.8 25.0 pectolytic enzyme (wt%) 0.007 0.01 0.05 protease (wt%) 0.03 0.075 0.01 lipase (wt%) 0.005 amylase (wt%) 0.01 0.005 0.001 PB1 (wt%) 1.6 7,8 PB4 (wt%) 6.9 11.4 nonionic (wt%) 1.2 2.0 1.1 TAED (wt%) 4.3 2.4 0.8 HEDP (wt%) 0.7 DETPMP (wt%) 0.65 paraffin (wt%) 0.4 0.5 BTA (wt%) 0.2 0.3 PA30 (wt%) 3.2 sulfate (wt%) 15.0 14.7 3.2 pH -1% solution 10.6 10.6 11.0

Example 18 *

···· • · ·· ♦ · · · • · · « • 9 9 99·

The following liquid dishwashing detergents I and II with a density of 1400 kg/m ³ were prepared using the procedures according to this invention:

II

STPP (wt%) 33.3 20.0 carbonate (wt%) 2.7 2.0 silicate (wt%) 4.4 NaDCC (wt%) 1.1 1.15 nonionic (wt%) 2.5 1.0 paraffin (wt%) 2.2 pectolytic enzyme (wt%) 0.005 0.05 protease (wt%) 0.03 0.02 amylase (wt%) 0.005 0.0025 48ON (wt%) 0.5 4.00 potassium hydroxide (wt%) 6.00 sulfate (wt%) 1.6 pH -1% solution 9.1 10.0

4· > 4 4 4 » · 4 4 •44 *··

4

44

Example 19

The following liquid cleaning preparations for cleaning solid surfaces were prepared according to the procedures of this invention:

AND II III IV IN VI pectolytic enzyme (wt%) 0.005 0.01 0.02 0.02 0.005 0.005 amylase (wt.%) 0.01 0.002 0.005 0.02 0.001 0.005 protease (wt.%) 0.05 0.01 0.02 0.03 0.005 0.005 EDTA ¹ (wt%) 2.90 2.90 Citrate (wt%) 2.90 2.90 LAS (wt%) 1.95 1.95 1.95 C12 AS (wt%) 2.20 2.20 2.20 NaCl2 (ethoxy)sulfate ² (wt%) 2.20 2.20 2.20 C12 dimethylamine oxide (wt%) 0.50 0.50 0.50 SCS (wt%) 1.30 1.30 1.30 hexylcarbitol ² (wt%) 6.30 6.30 6.30 6.30 6.30 6.30 water and other various ingredients up to 100%

¹ sodium salt of ethylenediaminetetraacetic acid ² hexyloxydi(ethyleneoxy) derivative ·· *· • · · • · · ··· ··· • · «· ··

Example 20

The following spray cleaning products were prepared using the procedures according to this invention, intended for cleaning solid surfaces and for removing dirt in the home:

AND

pectolytic enzyme (wt%) 0.01 amylase (wt.%) 0.01 protease (wt.%) 0.01 sodium octyl sulfate (wt%) 2.00 sodium dodecyl sulfate (wt%) 4.00 sodium hydroxide (wt%) 0.80 sodium silicate (wt%) 0.04 perfume 0.35

water and other various ingredients up to 100%

Claims (14)

PATENT CLAIMS A detergent comprising a pectolytic enzyme, characterized in that the enzymatic activity of the enzyme at a pH in the range of 7 to 11 is at least 10%, preferably 25%, more preferably 40% of its optimal enzymatic activity. 2. A detergent composition according to claim 1, wherein said pectolytic enzyme has an optimum activity at a pH in the range of 7 to 11; Detergent according to claims 1 and 2, characterized in that the concentration of said pectolytic enzyme is 0.0001 to 2% by weight, preferably 0.0005 to 0.5% by weight, more preferably 0.001 to 0.1% by weight. %, based on the total weight of the detergent. Detergent according to any one of the preceding claims, further comprising a dispersant. Detergent according to any one of the preceding claims, characterized in that it further comprises another enzyme used in detergents. 6. Detergent according to claim 5, characterized in that said other enzyme is selected from the group consisting of cellulase, protease, lipase and / or amylase. 7. A detergent composition according to any preceding claim, further comprising an enzymatic bleach system. Detergent according to any one of the preceding claims, further comprising a conventional activated bleaching system with a manganese-based bleach catalyst. A detergent according to any preceding claim, further comprising a dye transfer inhibiting polymer. • · »» A detergent according to any of the preceding claims, wherein the detergent is a liquid, paste, gel, or solid in the form of bars, tablets, powder or granules. 11. A detergent additive comprising a pectolytic enzyme, characterized in that the enzymatic activity of the enzyme is at least 10%, preferably 25%, more preferably 40% of its optimal enzymatic activity at a pH in the range 7-11. Use of a detergent according to any one of the preceding claims for cleaning fabrics and / or for removing stains on fabrics and / or for maintaining fabric whiteness and / or for softening fabrics and / or for maintaining the color appearance of fabrics and / or inhibiting dye transfer. Use of the detergent according to claims 1 to 11 for cleaning solid surfaces such as floors, walls, tiles and the like. Use of the detergent according to claims 1 to 11 for manual dishwashing and for dishwashing.