FI86884C - TVAETTMEDELSKOMPOSITIONER INNEHAOLLANDE CELLULAS - Google Patents

Abstract

Detergent compositions comprising detergent cellulases are disclosed. The compositions are formulated to provide a near-neutral or mildly-alkaline wash liquor pH. The compositions comprise a clay soil removal polymer and, optionally, a fabric-softening clay.

Description

1 86884

Detergent compositions containing cellulase

The present invention relates to detergent compositions comprising detergent cellulase and small amounts of a well-defined polymer. Preferred compositions also contain fabric softening clay.

The invention relates to detergent compositions containing detergent cellulase. The compositions are formulated to provide a wash liquor having a near neutral pH or slightly basic pH. They contain small amounts of a well-defined soil release polymer.

The use of cellulolytic enzymes, i.e. cellulase, as a roughness reducing agent in fabric softening compositions is described 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 57108-199.

EP-A 0120 528 discloses basic fabric softener compositions comprising a synergistic mixture of a water-insoluble tertiary C10-26 amine and cellulase.

EP-A 0 177 165 describes basic emollient compositions comprising a mixture of smectite clay and cellulase.

25 To date, however, detergent cellulases have not just been approved in the detergent industry. One reason is that little is known about the interaction between cellulase and other, more conventional ingredients in detergents. Another reason is that the compositions formulated according to the prior art do not use cellulase in its optimal pH range.

Until now, efforts have also been made to raise the pH (well above 10) in order to improve the cleaning ability of the formulated detergent compositions and in particular the removal of clay-based stains. But in such a basic pH range, the performance of commercial detergent cellulases is not optimal, so there is a constant need to formulate compositions with a pH below 10, with optimal performance of the cellulase, and still have good clay-soil cleaning ability.

The present invention responds to the need described above by providing effective, near neutral or mildly basic detergent compositions which have good cleaning performance, especially in cotton fabrics.

EP-A 0 112 593 describes alkylated amines which, when used in detergent compositions, have the effect of removing and re-precipitating clayey dirt. EP-A 0 137 615 describes liquid detergent compositions containing solvent-based alkoxylated polyamines.

The present invention relates to detergent compositions comprising a surfactant and a detergent cellulase. The detergent compositions of the invention are characterized in that they contain 0.1 to 1% of an alkoxylated polyamine as defined below, and that the pH of a 1% solution of the detergent compositions in distilled water is 6.5 to 9.5. Detergent compositions which further contain 1 to 10% of a fabric softening clay, preferably bentonite clay, are preferred. Also preferred are compositions that are substantially free of water-insoluble long chain alkylamines or derivatives thereof.

The detergent cellulase is preferably a bacterial or fungal cellulase having an optimum pH in the range of 5 to 30 11.5, more preferably 6.5 to 9.5. The amount of cellulase in the composition is preferably such that the cellulase activity of the composition is 5 to 100 CMCase units / g of composition.

Also preferred are compositions containing 0.5 to 5% of a water-soluble quaternary ammonium compound.

3 86884

In order to achieve optimal performance of detergent cellulases, it is preferred to formulate detergent compositions having a pH of a 1% aqueous solution in the range of 6.5 to 9.5. As expected, the clay-5 dirt removal ability of such compositions is relatively poor compared to compositions formulated to have a wash liquor pH of 10 or greater.

Certain water-soluble, quaternary ammonium compounds are highly preferred cationic keratensides in detergent compositions because these compounds have important greasy soil removal ability, but due to their positive charge, these cationic surfactants have a negative effect on the clay soil removal ability of the detergent composition. This effect is more pronounced at relatively Mata-15 at pH, where clay particles do not pepticize due to the probing effect of a negative charge, such as at pH above 10.

It has now been found that relatively small amounts of a well-defined alkoxylated polyamine polymer acting as a clay soil remover can prevent the negative effect on clay soil removal capacity occurring at pH 9.5 or lower and the negative effect due to the interaction of water-soluble quaternary -25 with den. In addition, it has been found that the presence of this clay soil release polymer in said pH range does not affect the precipitation of clays which can be used as fabric softeners (e.g. bentonite clays).

Accordingly, the preferred compositions of this invention address the contradictory situation of requiring the removal of clayey dirt while not affecting the precipitation of the desired emollients. The very surprising result obtained with them is probably due to the relatively small amounts of clayey soil release polymer which are sufficient to achieve a satisfactory removal of clayey 86884 4 dirt with the compositions of the present invention.

Surfactant I The surfactant 5 useful in this patent application preferably contains at least 50% by weight, more preferably 60-100% by weight of a surfactant which is an anionic surfactant (in its salt form) and which is not soap. A wide variety of anionic surfactants can be used in the compositions of the present invention. The total amount of surfactant may be in the range of about 0-95% by weight, preferably about 10-40% by weight, and most preferably about 15-30% by weight.

Suitable anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, alkyylipolyetoksieette-ether sulfate, paraffin sulfonates, alpha-sulfonates olefiinisulfo-15, alpha-sulphocarboxylates and their esters, alkyyllglyseryylieetterisulfonaattien, rasvahappomonogly-seridisulfaattien and sulfonates, alkyylifenolipolyetok-sieetterisulfaattien, 2-acyloxy-alkane-l-sulfonates and water-soluble salts of beta-alkyloxyalkane sulfonates.

Particularly preferred alkylbenzene 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 12 to 18 carbon atoms and an average of 1 to 12 -C 1-4 groups per molecule. In particular, alkyl chains have 10 to 16 carbon atoms and the molecule has an average of 1 to 6 -CH 2 CH 2 groups.

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 10 to 24, especially 14 to 16 carbon atoms. Alpha-olefin sulfonates can be prepared by reaction with sulfur trioxide, followed by neutralization 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 alpha-sulfonated fatty acids but also their esters formed with alcohols having from 1 to 14 carbon atoms.

Suitable alkyl glyceryl ether sulfonates include ethers of alcohols having from 10 to 18 carbon atoms, especially those derived from coconut oil and tallow. Suitable alkyl chains of polyphenol polyethoxy ether sulfates have 8 to 12 carbon atoms in the chain and have an average of 1 to 6 -Cl 2 CH 2 groups per molecule. Suitable acyl groups of 2-acyloxyalkane-1-sulfonates have 2 to 9 carbon atoms and 9 to 23 carbon atoms in the alkane moiety. Suitable beta-alkyl-oxyalkanesulfonates have 1-3 carbon atoms in the alkyl group and 8-20 carbon atoms in the alkane moiety.

The alkyl chains of the above anionic surfactants can be derived from natural sources such as coconut oil or tallow and can be synthesized by the Ziegler or Oxo-20 process. Water solubility is achievable with an alkali metal, ammonium or alkanol ammonium cation; sodium is preferred. The present invention also encompasses mixtures of anionic surfactants and a satisfactory mixture consists of an alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group and an alkyl sulfate having 12 to 18 carbon atoms in the alkyl group.

Non-ionized surfactants may be added to the compositions discussed herein in small amounts (less than 50%). Suitable non-ionic surfactants, including, but not limited to, HLBs of 11.5 to 17.0, include primary and secondary C 1 -C 10 alcohol ethoxylates and C 8 -C 10 alkylphenol ethoxylates. Linear, primary C 1 -C 6 alcohols condensed with 7 to 30 moles of ethylene oxide per mole of alcohol are preferred. Examples 35 are C14-C15 (EO) 7, Clg-C18 (EO) 25 and especially C16C18 (E0) 11 * 6 86884

In addition to anionic surfactants, other types of surfactants can be used in small amounts. These include zwitterionic, amphoteric and cationic surfactants.

Cationic keratensides useful in this patent application include water-soluble, quaternary ammonium compounds of the formula R 1, R 2, R 8, N 2, wherein R 2 is alkyl of 10 to 20, preferably 12 to 18 carbon atoms, and R 1 -, R 8 and R 6 are independently C 1 -C 4 alkyl and X is an anion, e.g. chloride. Examples of such trimethylammonium compounds are C 1-4 C 1-4 alkyltrimethylammonium chloride and coconut alkyltrimethylammonium methosulfate.

polyamines

Alkoxylated polyamines, which are suitable clay-dirt removal and reprecipitation inhibitors, and their preparation are described in EP-PA 0 112 593, which is incorporated herein by reference.

It should be noted that the term "polyamines" as used herein refers to generically alkoxylated 2Q polyamines in both their amine form and in their quaternized form. Such materials can be conventionally represented as molecules whose empirical formulas consist of repeating units: 25 - / NR 4 - amine form (alkoxy) and 3 ° f * - / • N -r 7 - X quaternized form I n (alkoxy) y 1 where R is a hydrocarbon group , usually having 7 to 86884 2-6 carbon atoms, may be a C 1 -C 20 hydrocarbon, the alkoxy groups are ethoxy, propoxy and the like, and y is 2-30, most preferably 10-20, n is an integer of at least 2, preferably 2- 20, most preferably 3-5, and X- is an anion, e.g.

5 halide or methyl sulfate formed in the quaternization reaction.

The most preferred polyamines used in this connection are the so-called ethoxylated polyethyleneimines, i.e. the product of the polymerization reaction of ethylene oxide and ethyleneimine with the general formula (EtO) - [n-CH2_CH2 JR-N_ (EtO) y 15 <Et0>, (Et °> y where EtO represents an ethylene oxide group - (OCH 2 Cl 2), n is an integer from 3 to 5 and y is an integer from 10 to 20.

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

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 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 Aero-30 monas. , and cellulase extracted from the liver and pancreas of an marine mollusc (Dolabella auricula Solanter).

The cellulase to be added to the composition of the invention may be in the form of a non-dusting granular mass, e.g. granular granules, or in the form of a liquid in which the cellulase is suspended as a concentrate 8 86884 suspended, e.g.

The determination of cellulase activity used herein is based on its ability to hydrolyze carboxymethyl-5 cellulose. The small molecule reducing carbohydrates formed are determined colorimetrically by the ferrocyanide method described by W.S. Hoffman *. "J. Biol. Chem.", 120, 51 (1973). The main parameters of the incubation are pH 7, temperature 40 ° C and incubation time 20 minutes.

A unit of CMCase is defined as the amount of enzyme that produces the amount of reducing carbohydrates per minute corresponding to 10 moles of glucose under the conditions described above.

In the present context, a highly preferred range of cellulase activity is 5 to 100 CMCase activity units / g of composition.

Preferred compositions discussed herein are substantially free of water-insoluble, long chain alkylamine plasticizers and derivatives thereof, as it has surprisingly been found that such compounds react negatively with cellulase in the pH range of the present invention. The general formula for amines incompatible with cellulase is R 8 R 9 R 10 N 'wherein R 8 and R 6 are independently C 1 -C 8 alkyl and R 10 is hydrogen or C 1 -C 8 alkyl. Derivatives of these amines, e.g. the corresponding amides, also react negatively with cellulase.

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

Optional Ingredients In addition to the necessary ingredients, the compositions discussed herein may contain optional ingredients, which may be highly desirable.

For example, it is an advantage that the compositions discussed herein contain clay softeners in combination with cellulase. Such clay softeners are known in the detergent patent literature and are widely used commercially in both Europe and the United States. These clay softeners include various heat-treated kaolins and various multi-layer mectites. Preferred clay softeners are the soft-smectite clays described in DE Patent 2,334,899 and GB Patent 1,400,898, for which more detailed information can be found.

The most preferred clay softeners for fabrics comprise materials of bentonite origin. Bento-15 rivets are mainly montmorillonite-type clays and contain varying amounts of impurities, the concentration 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 1-20% and preferably 2-10%. Surprisingly, alk-2q oxypolyamines do not negatively affect the precipitation of softening clays.

It is also advantageous that the detergent compositions contain a detergent enhancer and / or a metal ion sequestrant. Compounds classified in the art as known detergent builders include nitric triacetates, polycarboxylates, citrates, water-soluble phosphates such as tripolyphosphate and sodium ortho- and pyrophosphate, and mixtures thereof. Metal ion sequestrants include all of the above and, in addition to 3q, ingredients such as ethylenediaminetetraacetate, aminopolyphosphonates, and a wide variety of other polyfunctional organic acids and salts, which, due to their abundance, cannot be further listed here. See U.S. Patent 3,579,454, which provides typical examples of the use of such materials in various cleaning compositions. Preferred polyfunctional organic acids useful herein include citric acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriamine-pentamethylenephosphonic acid.

Another group of detergent enhancers useful in the present invention consists of insoluble sodium aluminum silicates. Zeolite enhancers, with a particle size of 1 to 10 microns (e.g. zeolite A described in DE patent 2,422,655, 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 of the invention 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. Preferred are unsaturated fatty acids having 14 to 18 carbon atoms in the alkyl chain, and the most preferred is oleic acid. Similar soaps can also be used. The use of optional fatty acids / soaps is up to 20%.

The compositions of the invention may also contain compounds of the general formula R-CH (C00H) CH2 (C00H), i.e. succinic acid derivatives, wherein R is C10-20 alkyl or alkenyl, preferably C12-16) -; or R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents.

Succinate builders are preferably used in the form of their water-soluble salts, e.g. 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.

1λ 86884 Also useful as enhancers in the present invention are the compounds described in U.S. Patent 4,663,071, i.e. mixtures of tartrate monomeric acid and tartrate-dimer succinic acid in a weight ratio of monomeric succinic acid to di-5-succinic acid of 97: 3 to 40:80, preferably ti.

Another optional ingredient is bleach. Preferred are peroxy bleaches such as sodium perborate, commercially available as mono- and tetrahydrate, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.

Bleach activators can be used with the above peroxygen bleaches. Groups of bleach activators include esters, imides, imidazoles, ox-25 and carbonates. Preferred ingredients in these groups include methyl o-acetoxybenzoates, sodium p-acetoxybenzenesulfonates such as sodium 4-octanoyloxybenzenesulfonate, sodium 4-octanoyloxybenzene ethyleneazideazeteneazisenisenisenisenenesulfonate, bisulfonate, sulfonate, tetraacetylhexamethylenediamine, tetraacetylmethylenediamine.

Other highly preferred peroxy bleach activators described in U.S. Patents 4,483,778 and 2,539,130 include alpha-substituted alkyl or alkenyl esters such as, sodium 4- (2-chlorooctanoyloxy) benzenesulfonate, sodium 4- (3,5,5-trimetyyliheksanoyylioksi) benzene sulphonate. Suitable peroxyacids are also peroxyoxy bleach activators, e.g. those described in 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 crosslinking carbonyl group and L is a leaving group, especially oxybenzenesulfonate.

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

The compositions discussed herein may contain, in addition to the ingredients already mentioned, various other optional ingredients typically used in commercial products to enhance the appearance or impart other properties to the product. Typical ingredients include pH adjusters, perfumes, colorants, optical brighteners, soil suspending agents, hydrotropes and gelling agents, antifreeze / thaw stabilizers, bactericides, preservatives, antifoams and bleach stabilizers.

Form and Preparation of Compositions The detergent compositions of this invention may be in any physical state, e.g., granules, liquid, 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 coating. this material in those in which the substrate is, for example, a nonwoven or paper sheet.

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

Example I

35 Granular detergents were prepared with the following compositions: i3 86884

Ingredient Weight%

A B

Sodium linear C 1 -C 2 alkyl sulphonate 11.0 7.0 5 Sodium thalalkyl sulphate 5.0

Tallow alcohol ethoxylate

Sodium tripolyphosphate 24.0 23.5

Bentonite clay 8.5 6.4

Coconut trimethylammonium chloride - 1.6 10 Boric acid - 4.0

Cellulase (1350 CMC donor units / g) 3,03.5

Proteolytic enzyme

Clay-based soil release polymer 0.5 0.3

Sodium sulphate, minor constituents, water Remaining ad 100 pH (1% solution in distilled water) 8.7 9.0 ^ Toxylated polyamine of formula 20

(EtO) --- CH2 - CH2 N

(EtO) y (EtO) y 25 where n is 4 and y is 15.

The following granular compositions were also prepared: 14 86884

Ingredient Weight%

Example II Example III

Sodium linear C 1-2 alkylbenzenesulfonate 7.0 6.5 5 (N, C 1-4 fatty alcohol / 11 ethylene oxide condensate 1.0 0.5

Sodium sulphate

Sodium tripolyphosphate 24

Zeolite A - 26.0 10 Sodium nitrilotriacetate - 5.0

Bentonite clay 6.5 6.5

Cellulase 3.5 ^ x 3, S ^ X

Proteolytic enzyme

Sodium perborate tetrahydrate 20.0 20.0 15 TAElfe 1.2 3.0

Boric acid 4.0 4.0

Optical brightness

Clay soil removing polymer ^ xx 0.4 0.6 2Q Minor ingredients and water remaining pH (1% solution in distilled water) 9.0 9.0

xxx) As in Example I

uu I

J Corresponds to 47 CMCase units / g of composition 25 ^ Tetraacetylethylenediamine 15 86884

Example IV

The following liquid detergent composition was also prepared:

Ingredient Weight% 5 Linear C 1-4 alkylbenzenesulfonic acid 11.0

Coconut alkyl sulfate (TEA salt) 4.0

Thalium C 1-4 alcohol ethoxylate (EO 7) 10.0 10 Coconut fatty acid 10.0

Oleic acid 5, Q

Citric acid 1.0

Triethanolamine 4.0

Ethanol 6 Propanediol 1.5

Sodium hydroxide 3

Sodium formate 1

Cellulase 2, ^

Protease 0.6 20 Clay soil removing polymers * 0.3 Minor ingredients and water remaining * ·) Equivalent to 34 CMC donkey units / g composition

25 As in Example I

Claims (10)

1. Detergent composition for cleaning and softening fabrics, characterized in that it contains - surfactant, - detergent cellulase, - 0.1 1% clay-based dirt-releasing polymer, of the formula R 1 or - £ -N 2 - R 1 - X - X '(alkoxy) y (alkoxy) y where R is a 2-6 carbon atoms containing hydrocarbon, R1 is a Ολ_20 hydrocarbon, alkoxy belongs to the group ethoxy, propoxy, butoxy or mixtures thereof, y is 2 - 30, n is an integer of at least 2, and X 'is an anion, and the pH of a 1%: g in distilled water solution is 6.5 - 9.5. Composition according to claim 1, characterized in that the alkoxylated polyamine is a reaction product of ethylene oxide and ethyleneimine. 3. A composition according to claim 2, characterized in that the alkoxylated polyamine has the formula (EtO) y-f N-CH 2 -CH 2 Jt-N- (EtO) γ (EtO) γ (EtO) γ 9 868 84 where EtO represents an ethylene oxide group - (OCH2CH2), n is an integer of 3-5 and y is an integer of 10-20. 4. A composition according to claim 3, characterized in that the optimized pH of the cellulase is within the range 6.5 - 9.5. 5. A composition according to claim 1, characterized in that the activity of the cellulase is from 5 to 100 CMC ash units / g of composition. 6. A composition according to claim 1, characterized in that the surfactant contains 60-100% by weight of anionic surfactant. 7. A composition according to claim 1, characterized in that it additionally contains from 1 to 20% textile softening agent. Composition according to claim 1, characterized in that it additionally contains 0.5-5% water-soluble quaternary ammonium compound, of the formula R4R5R6R7N * X is independently C 1-4 alkyl and X 'is an anion. 9. A composition according to claim 1, characterized in that it does not substantially contain water-insoluble long-chain alkyl amines or derivatives thereof. Composition according to Claim 1, characterized in that the pH of a 1% by weight in distilled-water solution is 8.5 - 9.5.