FI91276C - Softening detergent composition containing cellulase - Google Patents

Abstract

The compositions disclosed herein clean well and at the same time act as textile softeners. They contain a cellulase enzyme and are formulated at a mild alkaline pH range.

Description

i 91276

Cellulase softening detergent composition

The present invention relates to detergent compositions which have a good cleaning ability and at the same time act as fabric softeners.

Many attempts have been made to formulate laundry detergent compositions which have good cleaning performance and softening properties for myds textiles. Thus, efforts have been made to add cationic textile softeners to detergent compositions based on anionic surfactants using various means to overcome the silent inherent antagonism of anionic and cationic surfactant species. For example, GB Patent 1,518,529 describes detergent compositions comprising an organic surfactant, builders, a particulate quaternary ammonium softener, and a sparingly water-soluble anti-dispersion agent that prevents the cationic dispersible from premature. Female sachet compositions are required to accept prescribed compromises of cleansing and softening properties. Another attempt to provide emollient detergent compositions has been the use of nonionic surfactants in place of anionic surfactants and with cationic emollients, and compositions of this type are described, for example, in GB Patent 1,079,388, German Patent Publication No. 12,209,607 and U.S. Patent No. 12,205,607. 763. However, it has been found that if a sufficiently nonionic surfactant is used to provide good cleaning ability, this will impair the softening ability of the cationic plasticizer, so that in this case a compromise between cleaning and softening ability must be accepted.

GB 1,514,276 recently discloses certain tertiary anines having two long chain alkyl or alkenyl groups and one ly-35 alkyl group and which are effective fabric softeners in detergent compositions.

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MyGs has sought to provide textile softening detergent compositions using smectite-type clays, as described in GB 1,400,898.

EP patent application 0 026 528 describes the use of water-insoluble, long-chain tertiary amines with a water-soluble cationic quaternary ammonium compound and / or a water-soluble aliphatic amine and optionally clays in alkaline detergent compositions as fabric softener compositions.

It has been attempted to use cellulolytic enzymes, i.e. cellulase, as a roughness reducing agent in fabric softening compositions, as disclosed in GB Patent 1,368,599.

The use of cellulase in detergent compositions is described in GB-A-2,075,028, GB-A-2,095,275, GB-A-2,094,826 and JP Patent 57,108-199.

EP-A-0 120 528 describes basic emollient detergent compositions consisting of a synergistic mixture of water-insoluble C10-C26 tert-amine and cellulase.

EP-A-177 165 describes basic emollient detergent compositions comprising a mixture of smectite clay and cellulase.

But to this day, detergent cellulases have hardly been approved in the detergent industry, and especially not in softening during washing. One reason is that little is known about the interaction between cellulase and other, more conventional ingredients in detergents. Another reason is that, according to recipes in the prior art, cellulase is not used in formulations formulated at its optimal pH range.

Up to this day, mytts have been attempted to raise the pH (well above 10) when formulating detergent compositions that soften during washing, to improve cleaning ability, especially in cotton fabrics, as the cleaning ability deteriorates at lower pH due to precipitation of softener ingredients.

But the basic pH range of nS creates problems such as fabric roughness, fabric damage or fading, i.e. there is a constant need to formulate compositions with a pH below 10, good fabric care and excellent softening ability and which still have good cleaning ability.

The present invention responds to the need described above by providing effective, slightly emulsifying emollient compositions having good fabric care and softening ability and good cleaning ability, especially in cotton fabrics.

The present invention addresses the problems of the prior art because of the use of a cellulase enzyme in the optimal pH range of activity and because it has been found, in excess, that the use of water-insoluble, long-chain amines, e.g., EPA 0 026 528 and EPA 0 120 528 described, in the presence of cellulase las-20, the softening ability of repeated washes was invented under mildly emasic conditions.

It has also been found that the content of anionic surfactants must be high in order to achieve the benefits of the co-turbines described herein.

The invention relates to a detergent composition for cleaning and softening fabrics, which composition comprises a surfactant and a detergent cellulase.

The composition is characterized in that the surfactant contains at least 50% by weight of anionic surfactant; composition 30 is substantially free of water-insoluble, long chain alkylamine plasticizers or derivatives thereof; the composition comprises a fabric softening clay material; and the pH of the 1% solution of the detergent composition in distilled water is in the range of 6.5 to 9.0.

The cellulase-containing emollient detergent compositions of the invention, which are rich in anionic surfactants, are formulated at a slightly alkaline pH (less than 10).

These cellulase softening detergent compositions contain essentially no water-insoluble, long-chain, amyl softening derivatives.

In addition, the detergent compositions according to the invention achieve good softening and cleaning ability and have a good fabric care effect.

Preferred compositions additionally contain clay emollients.

Tensldi

The surfactant useful in this patent application contains at least 50% by weight, preferably 60 to 100% by weight of anionic surfactant (in its salt form). In this context, anionic surfactants do not mean soaps. A wide variety of anionic surfactants can be used in the invention.

Suitable anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, alpha-sulfocarboxylate sulphonyl sulfonate sulfonates and racemic acid sulfate monoacetate sulfonates, alkyl glyceryl ether sulfonates, alkyl glyceryl ether sulfonates. water-soluble salts of 1-sulfonates and beta-alkyloxyalkane sulfonates.

Particularly preferred alkyl benzene sulfonates have 9 to 15 carbon atoms in a straight or branched chain, especially 11 to 13 carbon atoms. The alkyl chain of suitable alkyl sulfates has 10 to 22, especially 12 to 18 carbon atoms. Suitable alkyl polyethoxy ether sulfates have an alkyl chain of 10 to 18 carbon atoms and an average of 1 to 12 -CH 2 CH 2 groups per molecule. In particular, the alkyl-35 chain has 10 to 16 carbon atoms and the molecule has an average of 1 to 6 -CH 2 CH 2 groups.

91276 5

Suitable paraffin sulfonates are substantially straight and have from 8 to 24, in particular from 14 to 18, carbon atoms. Suitable alpha-olefin sulfonates have from 10 to 24, in particular from 14 to 16, carbon atoms. Alpha-olefin sulfonates can be prepared by reaction with sulfur trioxide, the residue of which is neutralized under conditions such that any sulfones are hydrolyzed to the corresponding hydroxyalkane sulfonates. Suitable alpha-sulfocarboxylates contain from 6 to 20 carbon atoms and include not only salts of 10 alpha-sulfonated fatty acids, but also their esters formed with alcohols having from 1 to 14 carbon atoms.

Suitable alkyl glyceryl ether sulphates are ethers of alcohols having from 10 to 18 carbon atoms, in particular those derived from coconut oil and tallow. Suitable alkylphenol polyethoxy ether sulfates have an alkyl chain of 8 to 12 carbon atoms and an average of 1-6 -CH 2 CH 2 - groups per molecule. Suitable 2-acyloxyalkane-1-sulfonates have an acyl group of 2 to 9 carbon atoms and an alkane moiety of 9 to 23 carbon atoms.

Suitable beta-alkyloxyalkane sulfonates have an alkyl group of 1 to 3 carbon atoms and an alkane moiety of 8 to 20 carbon atoms.

The alkyl chains of the anionic surfactants mentioned above can be derived from natural residues such as coconut oil or tallow or can be synthesized by the Ziegler or Oxo process. Water solubility is achievable with an alkali metal, ammonium or alkanol ammonium cation; sodium is preferred. The present invention provides mixtures of anionic surfactants and a satisfactory mixture consists of an alkylbenzenesulfonate having 11 to 13 carbon atoms in the alkyl group and an alkyl sulfate having 12 to 18 carbon atoms in the alkyl group.

35 non-ionic surfactants can be added to the compositions treated here as waxy paints (less than 50%).

6

Suitable non-ionic surfactants, with an HLB value of 11.5 to 17.0 (but not limited to), include primary and secondary C10-C20 alcohol ethoxylates and C6-C10 alkyl phenol ethoxylates. Linear, primary C14-C18 alcohols condensed with 7-30 moles of ethylene oxide per mole of alcohol are preferred. Examples are C14-C15 (E0) 7, C16-C18 (E0) 25 and in particular C18-C18 (E0) 21.

In addition to the anionic surfactant, other types of surfactants can be used as waxy paints. These include zwitterionic, amphoteric and cationic surfactants.

Cationic keratensides useful in this patent application include water-soluble quaternary ammonium compounds of the formula R 4 R 5 R 6 R 7 N * X ', wherein R 4 is alkyl of 10 to 20, preferably 12 to 18 carbon atoms, and R 5, R 6 and R 7 are each C 1 -C 7 alkyl, preferably methyl and X 'is an anion, e.g. chloride. Examples of such trimethylammonium compounds are C12-C14 alkyl trimethyl ammonium chloride and coconut alkyl trimethyl ammonium methosulfate.

The total content of surfactant active ingredient may be in the range of about 5 to about 95% by weight, preferably about 10 to about 40% by weight, and more preferably about 15 to 30% by weight.

cellulase

The cellulase useful in the invention may be any bacterial or fungal cellulase having an optimum pH range of 5 to 9.5.

Suitable cellulases are described in GB-A-2 075 028, GB-A-2 095 275 and DE-A-2 247 832.

Examples of such cellulases are the cellulases produced by the strain Humicola 30 insolens (Humicola grisea var. Thermoidea), in particular the strain Humicola DSM 1800 and the cellulases produced by the fungus Bacillus N, and the cellulase 212 produced by the fungus belonging to the genus Aeromonas extracted from the liver and pancreas of marine molluscs 35 (Dolabella auricula Solander).

91276 7

The cellulase to be added to the composition according to the invention may be in the form of a non-foamed granular mass, e.g. granular granules, in the form of a liquid in which the cellulase is suspended as a concentrate in e.g. non-ionized ten-zid or dissolved in an aqueous medium.

The determination of the activity of the cellulase used herein is based on its ability to hydrolyze carboxymethylcellulose. The small molecular reducing carbohydrates formed are determined colorimetrically by the ferrocyanide method 10 described by W.S. Hoffman, J. Biol. Chem., 12, 51 (1973). The most important incubation parameters are pH 7, temperature 40 ° C and incubation time 20 minutes.

The CMCase unit is the amount of ground enzyme that the amount of reducing carbohydrates generated in 15 minutes corresponds to 10 ~ 6 moles of glucose in excess of the conditions described.

In this context, a highly preferred range of cellulase activity is 5 to 100 CMCase activity units / gram of composition.

The compositions of the invention are substantially free of water-insoluble, long chain alkylamine plasticizers and derivatives thereof, as they have been found to overreact negatively with cellulase in the pH range of the invention. Derivatives of amine-25 plasticizers refer to the corresponding amide compounds. Such amine softeners are described, for example, in EP-A-0 026 528 and EP-A-0 120 528 and are in particular amines of the formula R 1 R 2 R 3 N, in which R 1 and R 2 are C 6 -C 20 alkyl chains and R 3 is 30 C -C 1-6 alkyl chain or hydrogen.

The compositions treated herein are formulated in the pH range of 6.5 to 9.5 as measured from a 1% solution of the composition in distilled water. In this pH range, the cellulases useful here have optimal performance.

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Optional ingredients

The compositions discussed herein, in addition to the claimed alneoslen, contain a variety of ingredients which may be highly tackable.

5 On eslm. advantageously that the compositions treated herein contain a clay softener in combination with cellulase. Such clay softeners are known in the detergent patent literature and are used commercially on a large scale in both Europe and the United States. These clay softeners include various lamp-treated kaolins and various multilayer smectites. Preferred clay softeners are the emollient smectite clays described in German Patent 23,348,899 and GB Patent 1,400,898, for which more detailed information can be found.

The most preferred clay softeners for fabrics are those of bentonite origin. Bentonites are the closest montmorillonite-type clays and contain varying Maaria impurities, the content and nature of which depend on the source of the clay material. In preferred compositions, the amount of plasticizer acids is at least 1%, generally 1 to 20% and preferably 2 to 10%.

It is also advantageous that the detergent compositions used during washing contain a detergent enhancer 25 and / or a metal ion sequestrant. Compounds classified in the art as known detergent builders include nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyrophosphate, and mixtures thereof. Metal ion sequestrants include all of the above and, in addition, substances such as ethylenediaminetetraacetate, aminopolyphosphonates, and a wide variety of other polyfunctional organic acids and salts, which, due to their abundance, cannot be listed in more detail here. See. U.S. Patent 3,579,454, which discloses typical examples of the use of such agents in various cleaning compositions. Preferred polyfunctional organic acids useful herein are citric acid, ethylenediaminetetramethylenephosphonic acid and diethylenetriamine pentamethylenephosphonic acid.

Another group of detergent builders useful in the invention consists of insoluble sodium aluminosilicates. Zeolite enhancers, particle size 1 to 10 (e.g. zeolite A), described in German Patent 24 22 655, are particularly preferred for use in compositions containing little or no phosphate. The amount of enhancer / sequestrant is generally 0.5 to 45% of the composition.

The compositions may also contain saturated or unsaturated fatty acids and similar soaps.

The alkyl chain of suitable saturated or unsaturated fatty acids has 10 to 18 carbon atoms. Unsaturated fatty acids having 14 to 18 carbon atoms in the alkyl chain are preferred, and oleic acid is most preferred. Corresponding soaps can be used for 20 myOs. The use of optional fatty acids / soaps is up to 20%.

The compositions may also contain compounds of the general formula R-CH (COOH) CH2 (COOH), i.e. succinic acid derivatives, wherein R is C10-C20 alkyl or alkenyl, preferably C12-C16, or R may be substituted by hydroxyl, sulfo, sulfoxy or sulfone substituents.

Succinate enhancers are preferably used in the form of their water-soluble salts, e.g. in the form of sodium, potassium, ammonium and alkanolammonium salts.

Selected examples of succinate enhancers include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like.

Useful enhancers include the compounds described in U.S. Pat. No. 4,664,071, i.e. mixtures of tartrate monomeric resin and tartrate dimeric acid in a weight ratio of monomeric resin and dimeric acid of 97: 3 to 20:80, preferably 95: 5 to 40:60.

The optional optional component is bleach.

Preferred are peroxyalkylated bases such as sodium perborate, commercially available as mono- and tetrahydrate, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.

Bleach activators can be used in connection with the above-mentioned peroxygen bleaching basins. Groups of bleach activators include esters, imides, imidazoles, oximes and carbonates. In these groups, preferred substances include methyl o-acetoxybenzoates, sodium p-acetoxybenzenesulfonates such as sodium 4-octanoyloxybenzene sulfonate, sodium 4-octanoyloxybenzenesulfonylethetenisethyleneazetenethyleneazeteneazeneacetene sulfonate, sulfonate, ra-acetylhexamethylenediamine, tetraacetylmethylenediamine.

Other highly preferred peroxy bleach activators described in U.S. Patents 4,483,778 and 4,539,130 include alpha-substituted alkyl or alkenyl esters such as sodium 4- (2-chlorooctanoyloxy) benzenesulfonate, sodium 4- (3,5,5-trimethylhexanoyl-25-oxy) benzenesulfonate. Suitable peroxyacids are mybs peroxy bleach activators, e.g. those described in published EP patent application 0 166 571, i.e. compounds of the general type RXAOOH and RXAL, wherein R is a hydroxycarbonyl group, X is a heteroatom, A is a silylating carbonyl group and A is a silylating carbonyl group group, especially oxybenzenesulfonate.

In addition to the cellulase used herein, other enzymes such as proteolytic, amylolytic or lipolytic enzymes may be used. In the liquid embodiments of the compositions treated herein, all of the commonly used enzyme stabilization systems 91276 11 can be used as a conventional feature in the art. Examples of suitable stabilizing systems are short-chain C 1 -C 4 carboxylic acid, in particular formic acid in combination with small amounts of calcium, boric acid and its water-soluble salts, and possibly in combination with polyols.

In addition to the ingredients already mentioned, the compositions may contain various other optional ingredients which are typically used in commercial products to improve the appearance or to give the product other properties. Typical ingredients are pH adjusting agents, perfumes, colorants, optical brighteners, soil suspending agents, hydrotropes and gelling agents, freezing / melting stabilizers, bactericides, preservatives, defoamers, bleach stabilizers.

Form and preparation of compositions

The detergent compositions of the invention may be in any physical state, e.g. as granules, liquid-20, paste or sheet. They can be prepared in any manner appropriate to their physical form by mixing the components, agglomerating them together, microencapsulating them, dispersing them in a liquid carrier, and reversibly adsorbing them to a non-particulate support or leaching agent therefrom, thereby the material is, for example, a nonwoven or paper sheet.

The following examples illustrate the present invention without limiting the scope of the invention.

30 Example I

A granular detergent composition was prepared using the following ingredients in said proportions:

Ingredient Weight%

Sodium linear C 1-6 alkylbenzene sulfonate 11.0

Sodium tallow alkyl sulphate 5.0 5 Tallow alcohol ethoxylate (EO 11) 0.3

Sodium tripolyphosphate 24.0

Bervtonite clay 8.5

Cellulase 3.0 *

Proteolytic enzyme 0.9 10 Sodium sulphate 40.0 V / odor components and water ad 100 pH, 1% solution dist. in water 8.7 * corresponds to a composition of 40 CMCase units / g.

The above-mentioned composition achieved a good cleaning ability as well as a good softening effect as well as a good fabric care effect (no fabric damage, color fading or roughening of the fabric was observed).

The following granular compositions were prepared from mybs: 20 Ingredient Weight%

Example II Example Ill

Sodium linear C12-alkyl benzene sulfonate 7.0 6.5 C 1 -C 4 fatty alcohol / ethyl ethylene oxide condensate 1.0 0.5

Sodium sulphate

Sodium tripolyphosphate 24

Zeolite A - 26.0

Sodium nitriloacetate - 5.0 30 Bentonite clay 6.5 6.5

Cellulase 3.5 ** 3.5 **

Proteolytic enzyme

Sodium perborate tetrahydrate 20.0 20.0 TAED * 1.2 3.0 35 Boric acid 4.0 4.0 91276 13

Alneosa Weight%

Esltn. il Eslm. III

Optimum brightness 0.3 0.5

Loose ingredients and water ad 100 5 pH, 1% solution dist. in water S 9.0 9.0 * Tetraacetylethylenediamine ** Corresponds to 47 CMCase unitsOS / g composition

The compositions of Examples I and II provided a good cleaning, softening and fabric care effect.

In the present invention, a very important plot is the pH of the detergent composition solution. In order to show that the laundry detergent composition according to the invention clearly differs from the detergents disclosed in the closest prior art EP patent application 177,165, 15 experiments have been performed showing that the choice of detergent composition pH is a critical factor in .

The following liquid washbasin composition was prepared in the experiment: 20 Ingredient Maara (wt%)

Linear (N-alkylbenzenesulfonic acid 10.0

Triethanolamine (TEA) 5.0

Sulphated coconut alcohol ethoxylate (E03) / 25 TEA salt 10.0

Cl2 "l5" raSva "alcoholietoJcsylaat1: i ^ E07 ^ 11/0

Coconut fatty acid 10.0

Oleic acid 3.0 1,2-propanediol 10.0 30 Boric acid 2.0

Citric acid 1.5

Emas (50%) 6.5 waxy ingredients and water ad 100

The cellulase 35 described in the present invention was added in amounts corresponding to 47 CMC endoase units / liter and 95 CMC endoase units / liter.

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The efficacy of the two compositions obtained was examined by monitoring their ability to remove C14 radiolabeled sodium carboxymethylcellulase (C14 CMC) from the fabric. The study used 5 methods described in EP patent application 350,098 to achieve the fabric softening / fabric care ability of the pulp cellulase. In the experiment, the following results were obtained for one fraction of the wash at 40 ° C at pH values of 8-10: 10 C14 CMC staining of the fabric CMC endoase lysine Amount / liter pH 47 95 8.0 21.0 27.0 9.0 16.0 19.3 15 9.5 8.3 10.7 10.0 5.9 10.6

From the experimental results presented, it appears that an increase in the pH of the detergent composition above pH 9.0 has a strong effect on the fabric softening / fabric care ability of the cellulase. The test results show a significant reduction in the fabric softening / fabric care ability of the cellulase at pH 9.0 and 9.5. Even doubling the amount of cellulase (from 47 CMC endoase units / liter to 95 CMC endoase units / 25 seeds / liter) does not result in the C14 CMC fabric removal values being achieved at pH 9.0 or below.

The compositions described in Examples 1 and 2 of EP patent application 177 165 have a pH of 9.3. The results of the above experiments confirm that EP patent application 177 165 does not disclose the criticality of the pH range according to claim 1 according to the invention in optimizing the cellulase properties in all respects, i.e. good cleaning ability, good softening ability and good fabric care effect.

Claims (7)

1. Detergent composition for cleaning and softening fabrics, which composition contains a surfactant and a detergent cellulase, characterized in that the surfactant contains at least 50% by weight of an anionic surfactant; the composition does not substantially contain water-insoluble, long-chain alkylamine plasticizers or derivatives thereof; the composition contains a fabric softening clay material; and pH of a 1% solution of the detergent composition in water is in the range of 6.5 - 9.0. 2. A composition according to claim 1, characterized in that the cellulase is a bacterial or fungal cellulase having an optimum pH in the range of 5 - 11.5. 3. A composition according to claim 1 or 2, characterized in that the cellulase is an alkaline cellulase having an optimum pH in the range of 6.5 - 9.5. Composition according to any one of claims 1-3, characterized in that the composition has a cellulase activity of 5 - 100 CMCas activity units per one gram of composition. Composition according to any one of claims 1-4, characterized in that the surfactant contains 60-100% by weight of an anionic surfactant. A composition according to claim 1, characterized in that the fabric softening clay material is present in a quantity of 1 to 20% by weight of the composition. 7. A composition according to claim 6, characterized in that the fabric-softening clay material is bentonite clay.